Organic small molecule semiconducting chromophores for use in organic electronic devices

ABSTRACT

Small organic molecule semi-conducting chromophores containing a pyridalthiadiazole, pyridaloxadiazole, or pyridaltriazole core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority benefit of U.S. Provisional Patent Application No. 61/416,251, filed Nov. 22, 2010. The entire content of that application is hereby incorporated by reference herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with United States government support under grant no. DE-DC0001009 awarded by the Center for Energy Efficient Materials of the Department of Energy and under grant no. N-00014-04-0411 awarded by the Office of Naval Research. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION

Solution-processed organic photovoltaic devices (OPV) have emerged as a promising energy technology due to their ease of processing, low-cost, and ability to be fabricated onto light-weight flexible substrates. Polymer based OPV's have by far been the most studied, and power conversion efficiencies (PCE's) above 6% have recently been reported for polymer:fullerene bulk heterojunction (BHJ) devices. On the other hand, solution processed small molecule BHJ devices have received far less attention. Such molecular heterojunctions (MHJ) have several advantages over their polymer counterparts, in that small molecules have well defined structures, are easily functionalized, are mono-disperse, are readily purified, and do not suffer from batch-to-batch variations. Reports of efficient solution processed MHJ devices have recently emerged that have utilized merocyanine dyes, squaraine dyes, isoindigo, and diketopyrrolopyrrole based chromophores as the light harvesting donor component with a fullerene acceptor. PCE's have reached upwards of 4% for such devices. While these results are encouraging, there still exits a need for the development of novel discrete light harvesting materials. Key parameters for effective small molecule donors include having broad and efficient optical absorption that extends into the near-IR region to maximize photon absorption, deep HOMO levels from −5 to −5.5 eV to maximize open circuit voltages, relatively planar structures for high charge carrier mobility, high solution viscosity and solubilizing side chains for solution to film processing. Additionally, it is important that novel structures have facile and highly tunable syntheses to enable rapid and cheap generation of molecular libraries.

The present invention seeks to address the need for improved light harvesting molecules for molecular heterojunction devices by providing novel and advantageous materials for use in such devices.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to organic non-polymeric semiconducting chromophores containing the pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine), pyridaloxadiazole (PO, [1,2,5]oxadiazolo[3,4-c]pyridine), or pyridaltriazole (P3N, 2-H-[1,2,3]triazolo[4,5-c]pyridine) (or a 2-substituted P3N derivative) organic structure for use in heterojunction devices, such as organic small molecule solar cells and transistors. In one embodiment, the present invention is directed to non-polymeric electron-donating and electron-accepting chromophores having a pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine), pyridaloxadiazole (PO, [1,2,5]oxadiazolo[3,4-c]pyridine), or pyridaltriazole (P3N, 2-H-[1,2,3]triazolo[4,5-c]pyridine) (or a 2-substituted P3N derivative) core structure. In another embodiment, the present invention is directed to optoelectronic devices comprising an active layer composition of a mixture of a non-polymeric light-harvesting electron-donating chromophore based on a PT, PO, or P3N core structure with an electron-accepting material, such as a fullerene, methanofullerene, rylene diimides or related π-conjugated organic electron acceptors. Organic or inorganic electron acceptors can be used. In another embodiment, the present invention is directed to optoelectronic devices comprising an active layer composition of a mixture of a non-polymeric light-harvesting electron-accepting chromophore based on a PT, PO, or P3N core structure with an electron-donating material. Organic or inorganic electron donors can be used. The present invention is also directed to methods of fabricating the devices by solution processing. In one embodiment, all active layers of the described optoelectronic devices are formed from solutions comprising of non-polymeric discrete organic materials.

In one embodiment, the invention embraces compounds of Formula I:

and, in additional embodiments, compounds of Formula Ia, Formula Ib, and Formula Ic:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

A₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

Each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In another embodiment, the invention embraces compounds of Formula II:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between 0 and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. In another embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula II, X₁ and X₂ are each N and Y₁ and Y₂ are each CH. In some embodiments of Formula II, X₁ and X₂ are each CH and Y₁ and Y₂ are each N.

In some embodiments of Formula II, X₁ and X₂ are each N, Y₁ and Y₂ are each CH and each M is S. In some embodiments of Formula II, X₁ and X₂ are each CH, Y₁ and Y₂ are each N, and each M is S.

In some embodiments of Formula II, X₁ and X₂ are each N, Y₁ and Y₂ are each CH and each M is O. In some embodiments of Formula II, X₁ and X₂ are each CH, Y₁ and Y₂ are each N, and each M is O.

In preferred embodiments, B₂ is selected from the group consisting of a nonentity, H, F, a C₁-C₁₆ alkyl group, thiophene, benzothiophene, benzofuran, and benzothiazole.

In further embodiments, B₂ is phenyl, substituted at the p-position with diphenylamine (i.e., the B₂ moiety is triphenylamine)

In another embodiment, the invention embraces compounds of Formula II of Formula IIa, Formula IIb, or Formula IIc:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between 0 and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. In another embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula IIa, each M is S.

In some embodiments of Formula IIa, each M is O.

In some embodiments of Formula IIb, each M is S.

In some embodiments of Formula IIb, each M is O.

In some embodiments of Formula IIc, each M is S.

In some embodiments of Formula IIc, each M is O.

In some embodiments, the compounds of Formula II are selected from compounds of Formula IId:

where Q₁ is C or Si;

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N;

n is 0, 1, 2, or 3;

R₇ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl, benzothiophene-2-yl, and benzothiazole-2-yl; and

R₈ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C.

In one embodiment of Formula IId, Q₁ is Si.

In one embodiment of Formula IId, X₁ and X₂ are N and Y₁ and Y₂ are CH.

In one embodiment of Formula IId, X₁ and X₂ are CH and Y₁ and Y₂ are N.

In one embodiment of Formula IId, n is 2.

In one embodiment of Formula IId, R₇ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₇ is selected from benzofuran-2-yl.

In one embodiment of Formula IId, R₇ is selected from benzothiophene-2-yl.

In one embodiment of Formula IId, R₇ is selected from benzothiazole-2-yl.

In one embodiment of Formula IId, R₈ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₈ is selected from C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 1.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 1.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 1.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 1.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 2.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 2.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 2.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 2.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 3.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 3.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 3.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 3.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂ are CH, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂ are N, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In some embodiments of Formula II, the compounds are of Formula IIe:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N;

n is 0, 1, 2, or 3;

R₇ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl, benzothiophene-2-yl, benzothiazole-2-yl, 4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, 4,4-bis(C₁-C₁₆ alkyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, and 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl; and

R₉ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIe, n is 0.

In one embodiment of Formula IIe, n is 1.

In one embodiment of Formula IIe, n is 2.

In one embodiment of Formula IIe, n is 3.

In one embodiment of Formula IIe, X₁ and X₂ are N and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, X₁ and X₂ are CH and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula IIe, R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 0.

In one embodiment of Formula IIe, R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁ and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁ and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 0.

In one embodiment of Formula IIe, R₇ is n-hexyl.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ is n-hexyl.

In one embodiment of Formula IIe, R₇ is n-hexyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is n-hexyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is n-hexyl, X₁ and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is n-hexyl, X₁ and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is n-hexyl, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is n-hexyl, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 1.

In some embodiments, the compounds of Formula II embrace compounds of Formula IIf:

where R₉ is H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIf, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula IIf, R₉ is —O—(CH₂)₅CH₃.

In another embodiment, the invention embraces compounds of Formula III:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where H₁ is selected from A₁, —B₁—B₂, -A₁-B₁—B₂, or

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. In another embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula III of Formula IIIa, Formula IIIb, Formula IIIc, and Formula IIId:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′ silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of such groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. In another embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula IV-V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each E₁ is independently either absent, or selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole.

In one embodiment of Formula IV-V, each M is S. In one embodiment of Formula IV-V, each D₁ is the same moiety. In one embodiment of Formula IV-V, each D₂ is the same moiety. In one embodiment of Formula IV-V, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IV-V, each M is S, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH. In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is S. In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is S.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is O. In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is O.

In another embodiment, the invention embraces compounds of Formula IV-V of Formula IV:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole.

In one embodiment of Formula IV, each M is S. In one embodiment of Formula IV, each D₁ is the same moiety. In one embodiment of Formula IV, each D₂ is the same moiety. In one embodiment of Formula IV, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IV, each M is S, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH. In some embodiments of Formula IV, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is S. In some embodiments of Formula IV, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is S.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is O. In some embodiments of Formula IV, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is O.

In another embodiment, the invention embraces compounds of Formula IV of Formula IVa or Formula IVb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole.

In one embodiment of Formula IVa, each M is S. In one embodiment of Formula IVa, each D₁ is the same moiety. In one embodiment of Formula IVa, each D₂ is the same moiety. In one embodiment of Formula IVa, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IVa, each M is S, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVa, each M is O. In one embodiment of Formula IVa, each D₁ is the same moiety. In one embodiment of Formula IVa, each D₂ is the same moiety. In one embodiment of Formula IVa, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IVa, each M is O, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVb, each M is S. In one embodiment of Formula IVb, each D₁ is the same moiety. In one embodiment of Formula IVb, each D₂ is the same moiety. In one embodiment of Formula IVb, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IVb, each M is S, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVb, each M is O. In one embodiment of Formula IVb, each D₁ is the same moiety. In one embodiment of Formula IVb, each D₂ is the same moiety. In one embodiment of Formula IVb, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula IVb, each M is O, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In another embodiment, the invention embraces compounds of Formula IV-V of Formula V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole.

In one embodiment of Formula V, each M is S. In one embodiment of Formula V, each D₁ is the same moiety. In one embodiment of Formula V, each D₂ is the same moiety. In one embodiment of Formula V, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁). In one embodiment of Formula V, each M is S, each D₁ is the same moiety, and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH. In some embodiments of Formula V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is S. In some embodiments of Formula V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is S.

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂, and Y₃, are each CH, and each M is O. In some embodiments of Formula V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M is O.

In another embodiment, the invention embraces compounds of Formula Va or Formula Vb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl and heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole, dithienophosphole, and carbazole.

In one embodiment of Formula Va, each M is S. In one embodiment of Formula Va, each E₁ is the same moiety. In one embodiment of Formula Va, each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ is the same moiety. In one embodiment of Formula Va, each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other). In one embodiment of Formula Va, each M is S, and each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Va, each M is O. In one embodiment of Formula Va, each E₁ is the same moiety. In one embodiment of Formula Va, each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ is the same moiety. In one embodiment of Formula Va, each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other). In one embodiment of Formula Va, each M is O, and each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Vb, each M is S. In one embodiment of Formula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb, each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ is the same moiety. In one embodiment of Formula Vb, each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other). In one embodiment of Formula Vb, each M is S, and each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Vb, each M is O. In one embodiment of Formula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb, each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ is the same moiety. In one embodiment of Formula Vb, each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other). In one embodiment of Formula Vb, each M is O, and each E₁ is the same moiety, each D₁ is the same moiety, and each D₂ is the same moiety (where E₁, D₁, and D₂ are chosen independently of each other).

In another embodiment, the invention embraces compounds of Formula VI-VII:

where the moiety

is selected from

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ is CH, and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI-VII, each M is S. In other embodiments of Formula VI-VII, each M is O.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is S.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is O.

In some embodiments of Formula VI-VII, each F₁ is the same moiety. In some embodiments of Formula VI-VII, each G₁ is the same moiety. In some embodiments of Formula VI-VII, each G₂ is the same moiety. In some embodiments of Formula VI-VII, each F₁ is the same moiety, each G₁ is the same moiety, and each G₂ is the same moiety (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VI-VII, each F₁ is the same moiety, each G₁ is the same moiety, and each G₂ is the same moiety (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VI-VII, each F₁ is the same moiety, each G₁ is the same moiety, and each G₂ is the same moiety (where F₁, G₁, and G₂ are chosen independently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VI:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ is CH, and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI, each M is S. In other embodiments of Formula VI, each M is O.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is S.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is O.

In some embodiments of Formula VI, each F₁ is the same. In some embodiments of Formula VI, each G₁ is the same. In some embodiments of Formula VI, each G₂ is the same. In some embodiments of Formula VI, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VI, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VI, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VI, such as compounds of Formula VIa or Formula VIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIa, each M is S. In other embodiments of Formula VIa, each M is O. In some embodiments of Formula VIa, each F₁ is the same. In some embodiments of Formula VIa, each G₁ is the same. In some embodiments of Formula VIa, each G₂ is the same. In some embodiments of Formula VIa, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VIa, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VIa, each F₁ is the same, each G₁ is the same (where F₁, G₁, and G₂ are chosen independently of each other), and each G₂ is the same; and M is O.

In some embodiments of Formula VIb, each M is S. In other embodiments of Formula VIb, each M is O. In some embodiments of Formula VIb, each F₁ is the same. In some embodiments of Formula VIb, each G₁ is the same. In some embodiments of Formula VIb, each G₂ is the same. In some embodiments of Formula VIb, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VIb, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VIb, each F₁ is the same, each G₁ is the same (where F₁, G₁, and G₂ are chosen independently of each other), and each G₂ is the same; and M is O.

In another embodiment, the invention embraces compounds of Formula VII:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ is CH, and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VII, each M is S. In other embodiments of Formula VII, each M is O.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is S.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N, and each M is O.

In some embodiments of Formula VII, each F₁ is the same. In some embodiments of Formula VII, each G₁ is the same. In some embodiments of Formula VII, each G₂ is the same. In some embodiments of Formula VII, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VII, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VII, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VII, such as compounds of Formula VIIIa or Formula VIIIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl.

Each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

Each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups. Examples of aryl or heteroaryl groups include, but are not limited to, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIIa, each M is S. In other embodiments of Formula VIIa, each M is O. In some embodiments of Formula VIIa, each F₁ is the same. In some embodiments of Formula VIIa, each G₁ is the same. In some embodiments of Formula VIIa, each G₂ is the same. In some embodiments of Formula VIIa, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where G₁ and G₂ are chosen independently of each other). In some embodiments of Formula VIIa, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VIIa, each F₁ is the same, each G₁ is the same (where F₁, G₁, and G₂ are chosen independently of each other), and each G₂ is the same; and M is O.

In some embodiments of Formula VIIb, each M is S. In other embodiments of Formula VIIb, each M is O. In some embodiments of Formula VIIb, each F₁ is the same. In some embodiments of Formula VIIb, each G₁ is the same. In some embodiments of Formula VIIb, each G₂ is the same. In some embodiments of Formula VIIb, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other). In some embodiments of Formula VIIb, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is S. In some embodiments of Formula VIIb, each F₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosen independently of each other); and M is O.

In additional embodiments, the invention embraces compounds of Formula 1-2-3-4-5:

where P₁ is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₄ is selected from aryl or aryl substituted with alkyl, such as C₆-C₃₀ aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, and C₆-C₁₀ aryl groups optionally substituted with one or more C₁-C₁₆ alkyl groups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5;

In additional embodiments, the invention embraces compounds of Formula 1, Formula 2, Formula 3, Formula 4, or Formula 5:

In the structures for Formula 1, Formula 2, Formula 3, Formula 4, and Formula 5 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₄ is selected from aryl or aryl substituted with alkyl, such as C₆-C₃₀ aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, and C₆-C₁₀ aryl groups optionally substituted with one or more C₁-C₁₆ alkyl groups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5

In additional embodiments, the invention embraces compounds of Formula 6-7-8:

where P₂ is selected from:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl, such as C₆-C₃₀ aryl optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In additional embodiments, the invention embraces compounds of Formula 6, Formula 7, or Formula 8:

In the structures for Formula 6, Formula 7, and Formula 8 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl, such as C₆-C₃₀ aryl optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5.

In additional embodiments, the invention embraces compounds of Formula 9-10:

is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5 inclusive; and

where DONOR is as defined below.

In one embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5. In another embodiment, m is 0. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 5

In additional embodiments, the invention embraces compounds of Formula 9 or Formula 10:

In the structures for Formula 9 and Formula 10 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5 inclusive. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is 5. In another embodiment, m is 0. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 5; and

where DONOR is as defined below.

In the structures for Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9, and Formula 10 above, each DONOR moiety is independently selected from the following group:

where X is C or Si;

A is N or P;

R₁₁ is selected from C₁-C₁₆ alkyl;

R₁₂ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl;

R₁₃ is selected from C₁-C₁₆ alkyl or C₆-C₂₀ aryl;

R₁₄ is selected from C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, —C(═O)—O—C₁-C₁₆ alkyl, or —O—C(═O)—C₁-C₁₆ alkyl; and

R₁₅ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl; and

R₁₆ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl.

In further embodiments, in the structure for Formula 1-2-3-4-5, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 1, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 2, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 3, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 4, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 5, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 6-7-8, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 6, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 7, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 8, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 9-10, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 9, each DONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 10, each DONOR moiety is the same moiety.

In additional embodiments, the invention embraces electronic and optoelectronic devices comprising a non-polymeric compound, said compound incorporating one or more groups of Formula A:

where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device, where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl, and either X₁ is CH and Y₁ is N, or X₁ is N and Y₁ is CH. In one embodiment, where more than one moiety of Formula A is present, M, X₁, and Y₁ for each moiety is chosen independently of the other moiety or moieties. In another embodiment, where more than one moiety of Formula A is present, M is the same for each moiety, X₁ is the same for each moiety, and Y₁ is the same for each moiety.

In additional embodiments, the invention embraces electronic and optoelectronic devices comprising a non-polymeric compound, said non-polymeric compound incorporating a pyridalthiadiazole group, a pyridaloxadiazole group, or a pyridaltriazole group, wherein said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.

In additional embodiments, the invention embraces electronic and optoelectronic devices utilizing the compounds described above.

In additional embodiments, the invention embraces optoelectronic devices, such as organic solar cells, with the general device architecture using the compounds described above as a light harvesting electron donor, comprising:

1) a first hole-collecting electrode, optionally coated onto a transparent substrate;

2) an optional layer or layers adjacent to the first electrode, such as an electron-blocking, exciton-blocking, or hole-transporting layer;

3) a layer comprising a mixture of an electron acceptor, such as an organic electron acceptor or an inorganic electron acceptor, and an organic non-polymeric electron donor, said donor comprising one or more compounds selected from Formula I, Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9, or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and

5) a second electron-collecting electrode.

In additional embodiments, the invention embraces optoelectronic devices, such as organic solar cells, with the general device architecture using the compounds described above as a light harvesting electron acceptor, comprising:

1) a first hole-collecting electrode, optionally coated onto a transparent substrate;

2) an optional layer or layers adjacent to the first electrode, such as an electron-blocking, exciton-blocking, or hole-transporting layer;

3) a layer comprising a mixture of an electron donor, such as an organic electron donor or an inorganic electron donor, and an organic non-polymeric electron acceptor material selected from Formula I, Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9, or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and

5) a second electron-collecting electrode.

In additional embodiments, the invention embraces devices such as organic field-effect transistors with the general device architecture using the compounds described above as a hole transporting medium, comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrate is Si/SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, used to modify the surface energy of the dielectric and/or to facilitate deposition of the active layer;

3) an active layer comprising an organic non-polymeric hole transporting material selected from Formula I, Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9, or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

In additional embodiments, the invention embraces devices, such as organic field-effect transistors with the general device architecture using the compounds described above as an electron transporting medium, comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrate is Si/SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, used to modify the surface energy of the dielectric and/or to facilitate deposition of the active layer;

3) an active layer comprising an organic non-polymeric electron transporting material selected from Formula I, Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9, or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a UV-VIS-NIR absorption spectrum of compound 101 in CHCl₃ solution and of a film of compound 101 as-cast from CHCl₃ solution.

FIG. 2 shows a UV-VIS-NIR absorption spectrum of compound 102 in CHCl₃ solution and of a film of compound 102 as-cast from CHCl₃ solution.

FIG. 3 shows a UV-VIS-NIR absorption spectrum of compound 103 in CHCl₃ solution and of a film of compound 103 as-cast from CHCl₃ solution.

FIG. 4 shows a UV-VIS-NIR absorption spectrum of compound 104 in CHCl₃ solution and of a film of compound 104 as-cast from CHCl₃ solution.

FIG. 5 shows a UV-VIS-NIR absorption spectrum of compound 105 in CHCl₃ solution and of a film of compound 105 as-cast from CHCl₃ solution.

FIG. 6 shows a UV-VIS-NIR absorption spectrum of compound 106 in CHCl₃ solution and of a film of compound 106 as-cast from CHCl₃ solution.

FIG. 7 shows a UV-VIS-NIR absorption spectrum of compound 107 in CHCl₃ solution and of a film of compound 107 as-cast from CHCl₃ solution.

FIG. 8 shows a UV-VIS-NIR absorption spectrum of compound 108 in CHCl₃ solution and of a film of compound 108 as-cast from CHCl₃ solution.

FIG. 9 shows a UV-VIS-NIR absorption spectrum of compound 109 in CHCl₃ solution and of a film of compound 109 as-cast from CHCl₃ solution.

FIG. 10 shows a UV-VIS-NIR absorption spectrum of compound 110 in CHCl₃ solution and of a film of compound 110 as-cast from CHCl₃ solution.

FIG. 11 shows a UV-VIS-NIR absorption spectrum of compound 111 in CHCl₃ solution and of a film of compound 111 as-cast from CHCl₃ solution.

FIG. 12 shows a UV-VIS-NIR absorption spectrum of compound 112 in CHCl₃ solution and of a film of compound 112 as-cast from CHCl₃ solution.

FIG. 13 shows a UV-VIS-NIR absorption spectrum of compound 113 in CHCl₃ solution and of a film of compound 113 as-cast from CHCl₃ solution.

FIG. 14 shows a UV-VIS-NIR absorption spectrum of compound 114 in CHCl₃ solution and of a film of compound 114 as-cast from CHCl₃ solution.

FIG. 15 shows a UV-VIS-NIR absorption spectrum of compound 115 in CHCl₃ solution and of a film of compound 115 as-cast from CHCl₃ solution.

FIG. 16 shows a UV-VIS-NIR absorption spectrum of compound 116 in CHCl₃ solution and of a film of compound 116 as-cast from CHCl₃ solution.

FIG. 17 shows a plot of HOMO-LUMO energy levels.

FIG. 18 shows energy levels of an organic solar cell device using compound 103.

FIG. 19 shows data for solar cells fabricated using compound 103. Active layer thickness=75 nm. As-cast devices.

FIG. 20 shows data for solar cells fabricated using compound 103. Active layer thickness=75 nm. Thermally annealed devices.

FIG. 21 shows data for solar cells fabricated using compound 103. Active layer thickness=85 nm. As-cast devices.

FIG. 22 shows data for solar cells fabricated using compound 103. Active layer thickness=85 nm. Thermally annealed devices.

FIG. 23 shows data for solar cells fabricated using compound 103. Active layer thickness=105 nm. As-cast devices.

FIG. 24 shows data for solar cells fabricated using compound 103. Active layer thickness=105 nm. Thermally annealed devices.

FIG. 25 shows data (current-voltage curves) for additional solar cells fabricated using compound 103.

FIG. 26 shows data (EQE spectra) for additional solar cells fabricated using compound 103.

FIG. 27 shows data for 103:PC₇₁BM film blends.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Alkyl” is intended to embrace a saturated linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic hydrocarbon chain(s) and/or ring(s) having the number of carbon atoms specified, or if no number is specified, having 1 to 16 carbon atoms.

“Alkenyl” is intended to embrace a linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic hydrocarbon chain(s) and/or ring(s) having at least one carbon-carbon double bond, and having the number of carbon atoms specified, or if no number is specified, having 2 to 16 carbon atoms.

“Alkynyl” is intended to embrace a linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic hydrocarbon chain(s) and/or ring(s) having at least one carbon-carbon triple bond, and having the number of carbon atoms specified, or if no number is specified, having 2 to 19 carbon atoms, preferably 2 to 16 carbon atoms.

“Fluoroalkyl” indicates an alkyl group where at least one hydrogen of the alkyl group has been replaced with a fluorine substituent.

“Aryl” is defined as an optionally substituted aromatic ring system. Aryl groups include monocyclic aromatic rings, polyaromatic ring systems, and polycyclic aromatic ring systems containing the number of carbon atoms specified, or if no number is specified, containing six to thirty carbon atoms. In other embodiments, aryl groups may contain six to twenty carbon atoms, six to twelve carbon atoms, or six to ten carbon atoms. In other embodiments, aryl groups can be unsubstituted.

“Heteroaryl” is defined as an optionally substituted aromatic ring system. Heteroaryl groups contain the number of carbon atoms specified, and one or more heteroatoms (such as one to six heteroatoms, or one to three heteroatoms), where heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur, and phosphorus. In other embodiments, heteroaryl groups may contain six to twenty carbon atoms and one to four heteroatoms, six to twelve carbon atoms and one to three heteroatoms, six to ten carbon atoms and one to three heteroatoms, or three to six carbon atoms and one to three heteroatoms. In other embodiments, heteroaryl groups can be unsubstituted.

“Polymer” or “polymeric molecule” is defined herein as a structure containing at least eight repeating units. A “non-polymeric” molecule is a molecule containing seven or fewer repeating units. Thus, monomers, dimers, trimers, tetramers, pentamers, hexamers, and heptamers are non-polymeric molecules for the purposes of this disclosure. Interruption of a repeating unit “resets” the count of subunits for the purposes of this disclosure; thus, for example, for a molecule such as Formula 6:

when n is 5, the molecule is considered to have two separate five-subunit pieces, that is, it is comprised of two pentamers of thiophene, and is not considered a decamer or 10-subunit polymer of thiophene.

Non-polymeric molecules typically have a discrete molecular weight, while polymeric molecules typically have a distribution of molecular weights due to varying numbers of monomers that are incorporated into the growing chain during polymerization. Thus, in one embodiment, a preparation of a non-polymeric molecule will be characterized by a single molecular weight (where the molecular weight is averaged only over isotopic variation due to differing isotopes such as hydrogen, deuterium, carbon-12, carbon-13, etc.) of about 90%, preferably 95%, more preferably 98%, still more preferably 99%, of the molecular species. In contrast, preparations of a polymeric molecule will typically have a distribution of molecular weights due to varying numbers of monomers in the final polymer, where the molecular weight is an average over each individual polymeric species present in a given preparation (measured in either number-average molecular weight or weight-average molecular weight).

Small Molecule Chromophores

The current invention provides several advantages for preparation of optoelectronic devices. The organic materials described are non-polymeric allowing for synthesis and purification producers to be more repeatable than organic polymers. Unlike polymers, the organic materials described are discrete mono-disperse small molecules which allows for their exact structure to be known and reproduced. Synthesis of organic small molecule chromophores containing the pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine) organic structure is facile. Preparation of the PT organic structure can be found in M. Leclerc et al. Journal of the American Chemical Society, 2008, 130, 732. The asymmetry of the PT structure induced by the nitrogen atom in the aromatic backbone allows for facile mono-functionalization of the PT structure, forgoing numerous synthetic steps and purification procedures common with related symmetric structures. The organic small molecule chromophores described herein have relatively planar structures allowing for good inter-chromophore interaction, which facilitates charge transfer and transport.

The electronic properties of the pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine) compounds are favorable. The pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine) organic structure has an ideal electron affinity. Donor-acceptor organic materials based on this unit have favorable frontier molecular orbital levels (HOMO and LUMO) to accept and transport holes and electrons. The organic small molecule chromophores described also have favorable frontier molecular orbital levels (HOMO and LUMO) for use as electron donating materials in organic solar cell devices with fullerene, methanofullerene, rylene diimides or related π-conjugated organic electron acceptors. In addition, the organic small molecule chromophores described have favorable frontier molecular orbital levels (HOMO and LUMO) for use as electron accepting materials in organic solar cell devices with thiophene or phenyl based π-conjugated organic electron donors.

The optical properties of the pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine) compounds are also very good. The organic small molecule chromophores described have broad absorption spectra that absorb ultraviolet, visible, and near infrared radiation. The absorption spectra of the organic small molecule chromophores described have a favorable spectral overlap with the terrestrial solar spectrum, making them excellent light harvesting materials for organic solar cells.

The compounds are also readily handled in solution, as the organic small molecule chromophores described retain good solubility in many common organic solvents. This allows solution processing during the preparation of the optoelectronic devices.

While solution processing is preferred for its ease of handling and low cost, vapor deposition can also be used for PT, PO, or P3N molecules, or mixtures of said molecules with other components, which are suitable for use in such a method (e.g., vacuum deposition, physical vapor deposition, chemical vapor deposition).

Device Architectures, Materials, and Fabrication

In one embodiment, the optoelectronic device of the invention comprises the following layers:

a) a first hole-collecting electrode, optionally coated onto a transparent substrate;

b) an optional layer or layers adjacent to the first electrode, such as an electron-blocking, exciton-blocking, or hole-transporting layer;

c) a layer comprising a mixture of an electron donor of the general Formula I-VII and an electron acceptor (donor:acceptor);

d) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and

e) a second electron-collecting electrode.

Typically, the first electrode can be transparent, allowing light to enter the device, but in some embodiments, the second electrode can be transparent. In some embodiments, both electrodes are transparent.

Typically, the first electrode (layer “a”) is deposited onto a substrate, and the device is fabricated by subsequent deposition of layers “b” (if present), “c”, “d” (if present), and “e”. However, the second electrode “e” can be deposited onto a substrate, with subsequent deposition of layers “d” (if present), “c”, “b” (if present), and “a”.

In another embodiment, the optoelectronic device of the invention comprises the following layers:

a) indium tin oxide (ITO) coated onto a transparent substrate (a first electrode), where the transparent substrate can be glass, plastic, or any other transparent material compatible with ITO;

b) poly(3,4-ethylene dioxythiophene:poly(styrenesulfonate) (PEDOT:PSS) or a electron-blocking, exciton-blocking, or hole-transporting metal oxide, including, but not limited to, MoO3,

c) a mixture of electron-donating chromophores of the general Formula I-VII, and an electron-acceptor (donor:acceptor), and

e) a metal electrode (a second electrode); where layer (d) in the previous embodiment is absent.

Typically, the first electrode (layer “a”) is deposited onto the substrate, and the device is fabricated by subsequent deposition of layers “b”, “c”, and “e”. However, the second electrode “e” can be deposited onto a substrate, with subsequent deposition of layers “c”, “b”, and “a”.

The PT, PO, or P3N electron donors or electron acceptors can be used in tandem solar cells, such as those disclosed in US 2009/0126779. Tandem solar cells are arranged so that light which is not absorbed by a first solar cell passes to a second solar cell, where the second solar cell typically has a smaller bandgap than the first solar cell in order to absorb electromagnetic radiation that cannot be usefully absorbed by the first solar cell.

Passivating layers, such as those disclosed in US 2007/0221926 and US 2007/0169816, can be incorporated into devices using the PT, PO, or P3N electron donors or electron acceptors.

Optical spacer layers, such as those disclosed in US 2006/0292736, can also be employed in devices using the PT, PO, or P3N electron donors or electron acceptors.

In one configuration, where light passes though a transparent first electrode (such as ITO-coated glass), it is absorbed by the donor:acceptor mixture, which results in the separation of electrical charges and migration of the charges to the electrodes, yielding a usable electrical potential.

The first electrode can be made of materials such as indium-tin oxide, indium-magnesium oxide, cadmium tin-oxide, tin oxide, aluminum- or indium-doped zinc oxide, gold, silver, nickel, palladium and platinum. Preferably the first electrode has a high work function (4.3 eV or higher). Preferably, the first electrode is transparent.

The optional layer adjacent to the first electrode is preferably polystyrenesulfonic acid-doped polyethylenedioxythiophene (PEDOT:PSS). Other hole transporting materials, such as polyaniline (with suitable dopants), or N,N′-diphenyl-N,N′-bis(3-methylphenyl)[1,1′-biphenyl]-4,4′-diamine (TPD), nickel oxide, can be used. Electron-blocking, exciton-blocking, or hole-transporting metal oxides, such as MoO₃, MoO_(3-x), V₂O_(5-x), NiO, Ta₂O₅, Ag₂O, CuO, Cu₂O, CrO_(3-x), and WO₃, where x is between 0.01 and 0.99, more preferably between 0.1 and 0.9, can be used as materials between the hole-transporting electrode and the active layer. Other suitable materials are described in Greiner, Mark T. et al., “Universal energy-level alignment of molecules on metal oxides,” Nature Materials, DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

One method of fabricating the optoelectronic device is as follows: A conductive, transparent substrate is prepared from commercially available indium tin oxide-coated glass and polystyrenesulfonic acid doped polyethylenedioxythiophene using standard procedures. A solution containing a mixture of the donor and acceptor materials is prepared so that the ratio of donor to acceptor is between 1:99 and 99:1 parts by mass; more preferably between 3:7 and 7:3 parts by mass. The overall concentration of the solution may range between 0.1 mg/mL and 100 mg/mL, but is preferably in the range of 10 mg/mL and 30 mg/mL. In one embodiment of the invention, PT, PO, or P3N non-polymeric molecules are used that have a solubility of at least about 0.1 mg/mL in an organic solvent, 1 mg/mL in an organic solvent, 5 mg/mL, 10 mg/mL in an organic solvent, 30 mg/mL in an organic solvent, or 100 mg/mL in an organic solvent. The organic solvent can be selected from chloroform, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran, or carbon disulfide.

The electron acceptor is preferably [6,6]-phenyl C61-butyric acid methyl ester (PCBM), but may be a different fullerene (including, but not limited to, C71-PCBM), a tetracyanoquinodimethane, a vinazene, a perylene tetracarboxylic acid-dianhydride, a perylene tetracarboxylic acid-diimide, an oxadiazole, carbon nanotubes, or any other organic electron acceptor, such as those compounds disclosed in U.S. 2008/0315187.

In other embodiments, the electron acceptor is an inorganic acceptor selected from TiO₂ (titanium dioxide), TiO_(x) (titanium suboxide, where x<2) and ZnO (zinc oxide). The titanium dioxide can be anatase, rutile, or amorphous. A titanium dioxide layer can be prepared by depositing a sol-gel precursor solution, for example by spincasting or doctorblading, and sintering at a temperature between about 300° C. and 500° C. When an inorganic layer is used, component (c) of the optoelectronic device described above can be comprised of a layer of electron-donating chromophores of the general Formula I-VII and an inorganic electron-acceptor layer. Alternatively, the inorganic material can be dispersed in the electron-donating chromophores to create a single layer. Preparation of TiO₂ for use in solar cells is described in Brian O'Regan & Michael Gratzel, Nature 353:737 (1991) and Serap Günes et al., 2008 Nanotechnology 19 424009.

When titanium suboxide according to the formula TiO_(x) where x<2, is used, x is preferably 1<x<1.98, 1.1<x<1.9, 1.2<x<1.8, or 1.3<x<1.8. X in the formula TiO_(x) can be <2, <1.98, <1.9, <1.8, <1.7, or <1.6.

Useful solvents include chloroform, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran, and carbon disulfide. However, the solvent used may be any solvent which dissolves or partially dissolve both donor and acceptor materials and has a non-zero vapor pressure.

The solution of donor and acceptor is deposited by spin casting, doctor-blading, ink-jet printing, roll-to-roll coating, slot-dye coating, gravure coating, or any process which yields a continuous film of the donor-acceptor mixture such that the thickness of the film is within the range of 10 to 1000 nm, more preferably between 50 and 150 nm.

In certain embodiments, the layer of the donor and acceptor is cast from a solution comprising a solvent and the electron donor and the electron acceptor. The solvent can comprise chloroform, thiophene, trichloroethylene, chlorobenzene, carbon disulfide, a mixture of any of the foregoing solvents or any solvent or solvent mixture that dissolves both the donor and acceptor organic small molecule. The solvent can also include processing additives, such as those disclosed in US Patent Application Publication Nos. 2009/0032808, 2008/0315187, or 2009/0108255. For example, 1,8-diiodooctane (DIO) can be added to the solvent/donor/acceptor mixture in an amount of 0.1-10% by volume. The additive, such as 2% DIO, can be added to any organic solvent used to cast the layer of donor/acceptor, such as chloroform. The solvent can also include doping agents such as molybdenum trioxide (MoO₃). For example, MoO₃ can be added to the solvent/donor/acceptor mixture in an amount of 0.1-10% by volume.

An additional layer or layers of material (i.e., the layer(s) adjacent to the second electrode) may optionally be deposited on top of the donor-acceptor film in order to block holes or excitons, act as an optical buffer, or otherwise benefit the electrical characteristics of the device. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline can act as a hole-blocking or exciton-blocking material, while 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine and polyethylene dioxythiophene can act as exciton-blocking materials. Other materials that can be used between the second electrode and the active layer are titanium suboxide, ZnO, Cs₂CO₃, and ZrO₃. Additional materials suitable for use are described in Greiner, Mark T. et al., “Universal energy-level alignment of molecules on metal oxides,” Nature Materials, DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

Finally, an electrode, such as a metal electrode, is deposited on top of the structure by thermal evaporation, sputtering, printing, lamination or some other process. Conducting metal oxides, such as indium tin oxide, zinc oxide, or cadmium oxide, can also be used as electrodes, as well as conducting organic materials, such as electrodes comprising graphene. For metal electrodes, the metal is preferably aluminum, silver or magnesium, but may be any metal. Nanowires such as silver nanowires can also be used. If a transparent electrode is desired, very thin metallic sheets of metals can also be used. In some embodiments, the device is annealed before and/or after evaporation of the metal electrode.

Hole and electron mobilities are important parameters to consider in the fabrication/function of bulk heterojunction solar cells. For optimal device performance, a balance in the mobility of both charge carriers is desirable. Preferably, the electron and hole mobilities are both on the order of 10⁻⁴ cm²/Vs or higher. More preferably, the electron mobilities are on the order of 10⁻³ cm²/Vs or higher. In some embodiments, the electron mobilities are on the order of 10⁻⁴ cm²/Vs or higher, and the hole mobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vs or higher. In other embodiments, the electron mobilities are on the order of 10⁻³ cm²/Vs or higher, and the hole mobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vs or higher.

Optoelectronic devices of the present invention have excellent photovoltaic properties. In some embodiments, the power conversion efficiency (PCE) is at least 0.5%, at least 1.0%, at least 2.0%, or at least 3.0%. In some embodiments, the short circuit current density is greater than 3.0 mA/cm², and preferably greater than 8 mA/cm². In some embodiments, the open circuit voltage is between 0.3 and 1.0 V or higher. In some embodiments, the device exhibits an external quantum efficiency of approximately 35% or greater between 300 and 800 nm.

The morphological properties of the donor:acceptor films can be measured using atomic force microscopy or other surface-sensitive techniques. Preferably, the films will have a root-mean-squared surface roughness of less than 1.0 nm, more preferably less than 0.5 nm.

For embodiments of the devices using an inverted device architecture, the first electrode can comprise Au or another material having a work function higher than the work function of the second electrode, while the second electrode can comprise an ITO substrate modified using a self-assembled monolayer of 3-aminopropyltrimethoxysiloxane or another material having a work function lower than the work function of the first electrode.

EXAMPLES General Experimental Procedures

General Data:

Preparations were carried out on a bench top or under an atmosphere of dry, O₂-free N₂ employing both Schlenk line techniques and a Vacuum Atmospheres inert atmosphere glove box. Solvents (toluene, xylenes) were dried over sodium/benzophenone, distilled under vacuum, and stored over molecular sieves (4 Å). Solvents (chloroform) were dried over calcium hydride, distilled under vacuum, and stored over molecular sieves (4 Å). Molecular sieves (4 Å) were purchased from Aldrich Chemical Company and dried at 140° C. under vacuum for 24 hours prior to use. Deuterated solvents were dried over CaH₂ (CDCl₃) All reactants and reagents are commercially available and used as received unless otherwise noted.

Materials:

Compound 5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene {DTS(SnMe₃)₂} (Hou, J. H.; Chen, H. Y.; Zhang, S. Q.; Li, G.; Yang, Y. Journal of the American Chemical Society 2008, 130, 16144-16145) and 5′-Hexyl-2,2′-bithiophene-5-trimethylstannane (Parab, K.; Venkatasubbaiah, K.; Jakle, F. Journal of the American Chemical Society 2006, 128, 12879-12885) were prepared by methods similar to those reported in the literature. Compounds 5,5′-dibromo-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene (DTS-Br₂) and 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂) were purchased from Luminescence Technology Corp. (Lumtec) and used as received.

NMR:

¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy spectra were recorded on a Bruker Avance-500 MHz spectrometer at 25° C. unless otherwise noted. ¹H and ¹³C NMR spectra are referenced to SiMe₄ using the residual solvent peak impurity of the given solvent. Chemical shifts are reported in ppm and coupling constants in Hz as absolute values. DEPT, ¹H-¹H, and ¹H-¹³C correlation experiments were completed for assignment of the carbon atoms. ¹H-¹H NOE experiments were carried out with a mixing time of 0.8 seconds.

UV-vis-nearIR:

UV-visible spectra were recorded using either a Beckman Coulter DU 800 series or Perkin Elmer Lambda 750 spectrophotometer at room temperature unless otherwise noted. All solution UV-vis experiments were run in CHCl₃ under an N₂ atmosphere in Teflon-capped 1 mm quartz cuvettes. Films were prepared by spin-coating a 1% (w/w) solution of a compound of the invention, or a compound of the invention with PC₇₁BM, from CHCl₃ onto quartz substrates.

CHN:

Combustion analyses were performed by the MSI analytical lab at the University of California, Santa Barbara.

Electrochemistry:

All electrochemical measurements were performed using CHI instrument model 730B in a standard three-electrode, one compartment configuration equipped with Ag/AgCl electrode, Pt wire and Glassy carbon electrode (dia. 3 mm), as the pseudo reference, counter electrode and working electrode respectively. Glassy carbon electrodes were polished with alumina. The cyclic voltammetry (CV) experiments were performed in anhydrous acetonitrile (AcCN) solution with 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte at scan rate 100 mV/s unless otherwise stated. All electrochemical solutions were purged with dry Ar for 15 minutes at least to deoxygenate the system. Under these conditions, a Fc/Fc⁺ standard was calibrated to be 0.48 V. A mixture of small molecule in dry CHCl₃ (˜3 mg/mL) was used for preparation films at room temperature. Films were prepared by drop-cast onto Glassy carbon electrode for CV measurement.

Example 1

Synthesis of 7-bromo-4-thienyl[1,2,5]thiadiazolo[3,4-c]pyridine (ThPTBr)

A 20 mL microwave tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.51 g, 5.12 mmol), 2-(tributylstannyl)thiophene (Bu₃Sn—Th, 1.99 g, 5.33 mmol), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), toluene (10 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 40 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CH₂Cl₂ (500 mL). All volatiles were removed in vacuo to give the crude product as an orange solid. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as an orange solid. Recovered yield: 920 mg (60%). ¹H NMR (CD₂Cl₂): δ 8.67 (dd, ³J_(H-H)=4 Hz, ⁴J_(H-H)=1 Hz 1H, Th—CH), 8.63 (s, 1H, PT-CH), 7.64 (dd, ³J_(H-H)=4 Hz, ⁴J_(H-H)=1 Hz 1H, Th—CH), 7.26 (dd, ³J_(H-H)=5 Hz, ³J_(H-H)=4 Hz 1H, Th—CH), ¹³C{¹H} NMR (CD₂Cl₂): 156.90, 148.46, 147.96 (s, quaternary), 146.18 (s, CH), 141.65 (s, quaternary), 133.09 (s, CH), 131.74 (s, CH), 129.57 (s, CH), 108.91 (s, quaternary). Anal. Calcd. for C₉H₄BrN₃S₂: C, 36.25; H, 1.35; N, 14.09. Found: C, 36.6; H, 1.35; N, 13.8%. HRMS (EI) m/z, calcd for C₁₃H₇N₃S₃ (M⁺): 298.9. found: 299.

Synthesis of 101

A 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (M_(e3)Sn-SD_(TEH)-SnM_(e3), 961 mg, 1.29 mmol), 7-bromo-4-thienyl[1,2,5]thiadiazolo[3,4-c]pyridine (ThPTBr, 770 mg, 2.58 mmol), Pd(PP_(h3))₄ (0.050 g, 0.04 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 12⁰° C. for 3 minutes, 14⁰° C. for 3 minutes, and 17⁵° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% E_(t3)N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% E_(t3)N) gradient. After fraction collection and solvent removal a purple solid was obtained. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 980 mg (88%). ¹H NMR (C_(D2)C₁₂): δ 8.74 (s, 2H, PT-CH), 8.63 (d, ³ _(JH-H)=4 Hz, 2H Th—CH), 8.25 (t, 2H, SDT-CH), 7.60 (d, ³ _(JH-H)=4 Hz, 2H Th—CH), 7.27 (dd, ³ _(JH-H)=5 Hz, ³ _(JH-H)=4 Hz 2H, Th—CH), 1.59 (h, ³ _(JH-H)=6 Hz, 2H, CH), 1.38 (m, 4H, C_(H2)), 1.32 (m, 4H, C_(H2)), 1.25 (m, 8H, C_(H2)), 1.16 (m, 4H, SiC_(H2)), 0.86 (t, ³ _(JH-H)=8 Hz, 6H, C_(H3)), 0.83 (t, ³ _(JH-HH)=8 Hz, 6H, C_(H3)). ¹³{¹H} NMR (C_(D2)C₁₂): 155.06, 151.01, 148.44, 145.97, 142.57 (s, quaternary), 140.42 (s, CH), 139.02, 132.07 (s, CH), 131.79 (s, SDT-CH), 130.81 (s, CH), 129.37 (s, CH), 121.39 (s, quaternary), 36.70 (s, CH), 36.40 (s, SiC_(H2)), 29.59 (s, 2xC_(H2)), 23.62 (s, C_(H2)), 18.28 (s, C_(H2)), 14.54 (s, C_(H3)), 11.24 (s, C_(H3)). Anal. Calcd. for _(C42H44N6S6)Si: C, 59.12; H, 5.20; N, 9.85. Found: C, 59.0; H, 4.31; N, 9.32%. HRMS (EI) m/z, calcd for _(C42H44N6S6)Si (^(M+)): 852. found: 852. Absorbance: (CHCl₃) λ_(max)=582 nm, λ_(onset)=678 nm. (As Cast Film) λ_(max)=604, 652 nm, λ_(onset)=736 nm.

The UV-VIS-NIR absorption spectrum of 101 in CHCl₃ solution and of a film of 101 as-cast from CHCl₃ solution is shown in FIG. 1.

Example 2

Synthesis of 7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThPTBr)

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.41 g, 4.78 mmol), (5-hexylthiophen-2-yl)trimethylstannane (1.58 g, 4.78 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 30 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a red tacky solid. MeOH (100 mL) was added and the mixture sonicated for 5 minutes, followed by removal of MeOH in vacuo. The product was then slurried in MeOH (200 mL), filtered, washed with MeOH (200 mL), and dried under high vacuum for 24 hours. The product was collected as red solid. Recovered yield: 1.7 mg (94%). ¹H NMR (CDCl₃): δ 8.62 (s, 1H, PT-CH), 8.51 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 6.94 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 2.90 (t, 2H, ³J_(H-H)=8 Hz, Th—CH₂), 1.71 (tt, 2H, ³J_(H-H)=8 Hz, CH₂), 1.42 (br m, 2H, CH₂), 1.33 (br m, 4H, CH₂), 0.90 (m, 3H, ³J_(H-H)=8 Hz, CH₃). ¹³C{¹H} NMR (CDCl₃): 156.31, 153.21, 147.92, 147.65 (s, quaternary), 145.82 (s, CH), 138.19 (s, quaternary), 133.15, 126.56 (s, CH), 107.48 (s, quaternary), 31.53 (s, CH₂), 31.36 (s, CH₂), 30.58 (s, CH₂), 28.75 (s, CH₂), 22.54 (s, CH₂), 14.05 (s, CH₃). Anal. Calcd. for C₁₅H₁₆BrN₃S₂: C, 47.12; H, 4.22; N, 10.99. Found: C, 47.4; H, 4.03; N, 10.6%.

Synthesis of 102

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 510 mg, 0.68 mmol), 7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThPTBr, 574 mg, 1.50 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 562 mg (80%). ¹H NMR (CDCl₃): δ 8.70 (s, 2H, PT-CH), 8.43 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.18 (t, 2H, SDT-CH), 6.93 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 2.92 (t, ³J_(H-H)=7 Hz, 4H Th—CH₂), 1.79 (tt, ³J_(H-H)=7 Hz, 4H, CH₂), 1.59 (br m, 2H, CH), 1.44 (br m, 4H, CH₂), 1.35 (m, 14H, CH₂), 1.25 (m, 8H, CH₂), 1.19-1.08 (m, 4H, SiCH₂), 0.92 (m, 6H, CH₃), 0.88-0.83 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.51, 152.09, 150.27, 147.90, 145.05 (s, quaternary), 140.09 (s, CH), 139.23, 138.53 (s, quaternary), 132.03 (s, CH), 130.88 (s, CH), 126.40 (s, CH), 120.22 (s, quaternary), 36.08 (s, CH), 35.83 (s, CH₂), 31.61 (s, SiCH₂), 31.45 (s, CH₂), 30.62 (s, ThCH₂), 29.05 (s, CH₂), 28.98 (s, CH₂), 28.83 (s, CH₂), 23.08 (s, CH₂), 22.60 (s, CH₂), 17.79 (s, CH₂), 14.24 (s, CH₃), 14.10 (s, CH₃), 10.89 (s, CH₃). Anal. Calcd. for C₅₄H₆₈N₆S₆Si: C, 63.48; H, 6.71; N, 8.23. Found: C, 63.5; H, 6.65; N, 8.20%. Absorbance: (CHCl₃) λ_(max)=600 nm, λ_(onset)=700 nm. (As Cast Film) λ_(max)=620, 670 nm, λ_(onset)=760 nm.

The UV-VIS-NIR absorption spectrum of 102 in CHCl₃ solution and of a film of 102 as-cast from CHCl₃ solution is shown in FIG. 2.

Example 3

Synthesis of 7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThPTBr)

Suzuki: In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 550 mg, 1.86 mmol), Na₂CO₃ (1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (10 mL), and sealed with a Teflon® cap. To this mixture was added de-gassed de-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes. 5′-Hexyl-2,2′-bithiophene-5-boronic acid pinacol ester (773 mg, 2.05 mmol) in anhydrous THF (5 mL) was then added to the reaction mixture which was subsequently purged with Ar for 5 minutes. The reaction mixture was heated to 90° C. and vigorously stirred for 16 hours. Upon cooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20 minutes. The precipitate that formed was collect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH. The crude product was purified by flash chromatography eluting with a hexanes/CHCl₃ gradient. After fraction collection and solvent removal the resulting red solid was dried under high vacuum for 48 hours. The product was collected as red solid. Recovered yield: 555 mg (65%). Stille: In a N₂ filled glove box a 5 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 550 mg, 1.86 mmol), 5′-Hexyl-2,2′-bithiophene-5-trimethylstannane (770 mg, 1.86 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 25 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a red solid. The product was slurried in MeOH (200 mL), filtered, washed with MeOH (200 mL), and dried under high vacuum for 24 hours. The product was collected as red solid. Recovered yield: 750 mg (87%). ¹H NMR (CDCl₃): δ 8.62 (s, 1H, PT-CH), 8.56 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.21 (m, 1H, Th—CH), 7.17 (m, 1H, Th—CH), 6.74 (m, 1H, Th—CH), 2.83 (d, 2H, ³J_(H-H)=8 Hz, Th—CH₂), 1.71 (m, 2H, CH₂), 1.41 (m, 2H, CH₂), 1.33 (m, 4H, CH₂), 0.92 (m, 3H, CH₃). ¹³C{¹H} NMR (CDCl₃): 147.44, 147.26 (s, quaternary), 145.85 (s, CH), 143.86, 138.48, 134.32 (s, quaternary), 133.79 (s, CH), 128.63 (s, quaternary), 125.00, 124.58 (s, CH), 124.07 (s, quaternary), 31.57 (s, CH₂), 31.52 (s, CH₂), 30.30 (s, CH₂), 28.80 (s, CH₂), 22.61 (s, CH₂), 14.12 (s, CH₃). Anal. Calcd. for C₁₉H₁₈BrN₃S₃: C, 49.13; H, 3.91; N, 9.05. Found: C, 48.8; H, 3.60; N, 9.01%

Synthesis of 103

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 617 mg, 0.83 mmol), 7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThPTBr, 770 mg, 1.66 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 700 mg (71%). ¹H NMR (CDCl₃): δ 8.79 (s, 2H, PT-CH), 8.55 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.17 (t, 2H, SDT-CH), 7.23 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.20 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.75 (m, 2H, Th—CH), 2.84 (t, ³J_(H-H)=7 Hz, 4H Th—CH₂), 1.74 (h, ³J_(H-H)=6 Hz, 4H, CH), 1.60 (m, 2H, CH), 1.43 (m, 4H, CH₂), 1.31 (m, 14H, CH₂), 1.24 (m, 10H, CH₂), 1.13 (m, 4H, SiCH₂), 0.92 (m, 6H, CH₃), 0.85 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.55, 150.50, 148.03, 146.99, 145.19, 142.82 (s, quaternary), 140.17 (s, CH), 139.66, 138.58, 134.62 (s, quaternary), 132.70 (s, CH), 130.87 (s, CH), 125.22 (s, CH), 124.66 (s, CH), 124.60 (s, CH), 120.47 (s, quaternary), 36.05 (s, CH), 35.79 (s, CH₂), 31.57 (s, SiCH₂), 31.54 (s, CH₂), 30.29 (s, ThCH₂), 29.02 (s, CH₂), 28.99 (s, CH₂), 28.78 (s, CH₂), 23.05 (s, CH₂), 22.58 (s, CH₂), 17.75 (s, CH₂), 14.21 (s, CH₃), 14.08 (s, CH₃), 10.87 (s, CH₃). Anal. Calcd. for C₆₂H₇₂N₆S₈Si: C, 62.79; H, 6.12; N, 7.09. Found: C, 62.5; H, 6.00; N, 7.05%. HRMS (EI) m/z, calcd for C₆₂H₇₂N₆S₈Si (M⁺): 1184. found: 1184. Absorbance: (CHCl₃) λ_(max)=625 nm, λ_(onset)=725 nm, ∈=35000 cm⁻¹ M⁻¹. (As Cast Film) λ_(max)=655, 710 nm, λ_(onset)=795 nm.

The UV-VIS-NIR absorption spectrum of 103 in CHCl₃ solution and of a film of 103 as-cast from CHCl₃ solution is shown in FIG. 3.

Example 4

Synthesis of 7-bromo-4-(5-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThThPTBr)

Suzuki: In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 470 mg, 1.59 mmol), Na₂CO₃ (1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (10 mL), and sealed with a Teflon® cap. To this mixture was added de-gassed de-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes. 5′-Hexyl-2,2′,2″-trithiophene-5-boronic acid pinacol ester (729 mg, 1.59 mmol) in anhydrous THF (5 mL) was then added to the reaction mixture which was subsequently purged with Ar for 5 minutes. The reaction mixture was heated to 90° C. and vigorously stirred for 16 hours. Upon cooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20 minutes. The precipitate that formed was collect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH. The crude product was purified by flash chromatography eluting with a hexanes/CH₂Cl₂ gradient. After fraction collection and solvent removal the resulting red solid was dried under high vacuum for 48 hours. The product was collected as red solid. Recovered yield: 400 mg (46%). Stille: In a N₂ filled glove box a 5 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 197 mg, 0.67 mmol), 5′-Hexyl-2,2′,2″-trithiophene-5-trimethylstannane (330 mg, 0.067 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a red solid. The product was slurried in MeOH (200 mL), filtered, washed with MeOH (200 mL), and dried under high vacuum for 24 hours. The product was collected as red solid. Recovered yield: 310 mg (85%). ¹H NMR (CDCl₃): δ 8.64 (s, 1H, PT-CH), 8.59 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.26 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.24 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.05 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.03 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 6.71 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 2.80 (m, 2H, Th—CH₂), 1.67 (m, 2H, CH₂), 1.41 (m, 2H, CH₂), 1.34 (m, 4H, CH₂), 0.92 (m, 3H, CH₃).

Synthesis of 104

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 188 mg, 0.25 mmol), 7-bromo-4-(5-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThThPTBr, 290 mg, 0.53 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 250 mg (73%). ¹H NMR (CDCl₃): δ 8.74 (s, 2H, PT-CH), 8.50 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.14 (t, 2H, SDT-CH), 7.23 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.21 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.02 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.99 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.68 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 2.81 (m, ³J_(H-H)=7 Hz, 4H Th—CH₂), 1.70 (h, ³J_(H-H)=7 Hz, 4H, CH), 1.60 (m, 2H, CH), 1.40 (m, 4H, CH₂), 1.34 (m, 14H, CH₂), 1.27 (m, 10H, CH₂), 1.15 (m, 4H, SiCH₂), 0.91 (m, 8H, CH₃), 0.87 (m, 10H, CH₃). Absorbance: (CHCl₃) λ_(max)=645 nm, λ_(onset)=765 nm, ∈=36500 cm⁻¹ M⁻¹. (As Cast Film) λ_(max)=680 nm, π_(onset)=875 nm.

The UV-VIS-NIR absorption spectrum of 104 in CHCl₃ solution and of a film of 104 as-cast from CHCl₃ solution is shown in FIG. 4.

Example 5

Synthesis of 4-(benzo[b]thiophen-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzThPTBr)

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 510 mg, 1.73 mmol), Na₂CO₃ (1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (6 mL), and sealed with a Teflon® cap. To this mixture was added de-gassed de-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes. Benzothiophene-2-boronic acid (340 mg, 1.9 mmol) in anhydrous THF (6 mL) was then added to the reaction mixture which was subsequently purged with Ar for 5 minutes. The reaction mixture was heated to 90° C. and vigorously stirred for 16 hours. Upon cooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20 minutes. The precipitate that formed was collect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH (product is slightly soluble in MeOH). The solid was dried under high vacuum for 48 hours. The product was collected as an orange solid. Recovered yield: 410 mg (68%). ¹H NMR (CDCl₃): δ 8.99 (s, 1H, PT-CH), 8.74 (s, 1H, Th—CH), 7.94 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.91 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.74 (t, ³J_(H-H)=8 Hz, 1H, Bz-CH), 7.71 (t, ³J_(H-H)=8 Hz, 1H, Bz-CH). ¹³C{¹H} NMR (CDCl₃): 156.6, 148.4, 147.8 (s, quaternary), 145.7 (s, CH), 141.7, 141.1, 140.9 (s, quaternary), 130.3 (s, CH), 126.7 (s, CH), 125.5 (s, CH), 125.1 (s, CH), 122.5 (s, CH), 109.7 (s, quaternary). Anal. Calcd. for C₁₃H₆BrN₃S₂: C, 44.84; H, 1.74; N, 12.07. Found: C, 45.0; H, 1.46; N, 11.8%.

Synthesis of 105

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 395 mg, 0.53 mmol), 4-(benzo[b]thiophen-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzThPTBr, 374 mg, 1.07 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 350 mg (77%). ¹H NMR (CDCl₃): δ 8.77 (s, 2H, PT-CH), 8.64 (m, 2H Th—CH), 8.27 (t, 2H, SDT-CH), 7.88 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.85 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.34 (m, ³J_(H-H)=8 Hz, 4H, Bz-CH), 1.65 (h, ³J_(H-H)=6 Hz, 2H, CH), 1.43 (m, 4H, CH₂), 1.38 (m, 4H, CH₂), 1.31 (m, 8H, CH₂), 1.19 (m, 4H, SiCH₂), 0.92 (t, ³J_(H-H)=8 Hz, 6H, CH₃), 0.89 (t, ³J_(H-H)=8 Hz, 6H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.17, 150.75, 148.09, 145.50, 145.49, 145.08, 141.74 (s, quaternary), 141.20 (s, CH), 139.65 (s, quaternary), 138.60 (s, CH), 131.71 (m, SDT-CH), 128.82 (s, CH), 126.03 (s, quaternary), 125.04 (s, CH), 124.59 (s, quaternary), 122.39 (s, CH), 121.27 (s, CH), 36.13 (s, SiCH₂), 35.89 (s, CH), 29.10 (s, 2xCH₂), 23.11 (s, CH₂), 17.81 (s, CH₂), 14.27 (s, CH₃), 10.93 (s, CH₃). Anal. Calcd. for C₅₀H₄₈N₆S₆Si: C, 62.99; H, 5.07; N, 8.81. Found: C, 62.8; H, 4.59; N, 8.82%. HRMS (EI) m/z, calcd for C₅₀H₄₈N₆S₆Si (M⁺): 952. found: 952. Absorbance: (CHCl₃) λ_(max)=594 nm, λ_(onset)=696 nm. (As Cast Film) λ_(max)=620, 664 nm, λ_(onset)=758 nm.

The UV-VIS-NIR absorption spectrum of 105 in CHCl₃ solution and of a film of 105 as-cast from CHCl₃ solution is shown in FIG. 5.

Example 6

Synthesis of 4-(benzofuran-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzFuPTBr)

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 300 mg, 1.01 mmol), Na₂CO₃ (1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (6 mL), and sealed with a Teflon® cap. To this mixture was added de-gassed de-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes. Benzofuran-2-boronic acid (164 mg, 1.01 mmol) in anhydrous THF (6 mL) was then added to the reaction mixture which was subsequently purged with Ar for 5 minutes. The reaction mixture was heated to 90° C. and vigorously stirred for 16 hours. Upon cooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20 minutes. The precipitate that formed was collect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH. The crude product was purified by flash chromatography eluting with a hexanes/CHCl₃ gradient. After fraction collection and solvent removal the resulting orange solid was dried under high vacuum for 48 hours. The product was collected as orange solid. Recovered yield: 205 mg (61%). ¹H NMR (CDCl₃): δ 8.88 (s, 1H, PT-CH), 8.44 (s, 1H, Th—CH), 7.78 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.72 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.47 (dd, ³J_(H-H)=8 Hz, 1H, Bz-CH), 7.34 (dd, ³J_(H-H)=8 Hz, 1H, Bz-CH). ¹³C{¹H} NMR (CDCl₃): 152.2, 148.1, 146.2 (s, quaternary), 144.4 (s, CH), 141.2, 140.1, 138.3 (s, quaternary), 130.5 (s, CH), 125.5 (s, CH), 124.1 (s, CH), 123.8 (s, CH), 122.4 (s, CH), 110.2 (s, quaternary).

Synthesis of 106

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 93 mg, 0.12 mmol), 4-(benzofuran-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzFuPTBr, 83 mg, 0.25 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 59 mg (51%). ¹H NMR (CDCl₃): δ 8.97 (s, 2H, PT-CH), 8.35 (m, 2H Fu-CH), 8.25 (m, 2H, SDT-CH), 7.75 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.72 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.44 (dd, ³J_(H-H)=8 Hz, 2H, Bz-CH), 7.32 (dd, ³J_(H-H)=8 Hz, 2H, Bz-CH), 1.59 (h, ³J_(H-H)=7 Hz, 2H, CH), 1.40 (m, 4H, CH₂), 1.32 (m, 4H, CH₂), 1.26 (m, 8H, CH₂), 1.15 (m, 4H, SiCH₂), 0.86 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 155.63, 154.36, 151.23, 148.13, 145.63, 141.19 (s, quaternary), 140.16 (s, PT-CH), 138.36 (s, quaternary), 138.60 (s, CH), 131.71 (s, SDT-CH), 128.89 (s, quaternary), 126.18, 123.56, 122.32 (s, Bz-CH), 121.77 (s, quaternary), 113.53 (s, Fu-CH), 112.06 (s, Bz-CH), 36.07 (s, CH₂), 35.80 (s, CH), 29.02 (s, CH₂), 28.97 (s, CH₂), 23.06 (s, CH₂), 17.76 (s, CH₂), 14.21 (s, CH₃), 10.87 (s, CH₃). Anal. Calcd. for C₅₀H₄₈N₆O₂S₄Si: C, 65.18; H, 5.25; N, 912. Found: C, 65.2; H, 5.22; N, 9.14%. HRMS (EI) m/z, calcd for C₅₀H₄₈N₆O₂S₄Si (M⁺): 920. found: 920. Absorbance: (CHCl₃) λ_(max)=610 nm, λ_(onset)=695 nm. (As Cast Film) λ_(max)=625, 675 nm, λ_(onset)=760 nm.

The UV-VIS-NIR absorption spectrum of 106 in CHCl₃ solution and of a film of 106 as-cast from CHCl₃ solution is shown in FIG. 6.

Example 7

Synthesis of 4-(benzo[d]thiazol-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzTaPTBr)

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 710 mg, 2.40 mmol), 2-tributylstannylbenzothiazole (1.0 g, 2.36 mmol), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous Toluene (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as an orange solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal an orange solid was obtained. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as orange solid. Recovered yield: 442 mg (53%). ¹H NMR (CDCl₃): δ 8.90 (s, 1H, PT-CH), 8.40 (d, ³J_(H-H)=9 Hz, 1H Bz-CH), 8.03 (d, ³J_(H-H)=9 Hz, 1H Bz-CH), 7.59 (m, ³J_(H-H)=9 Hz, 1H, Bz-CH), 7.53 (m, ³J_(H-H)=9 Hz, 1H, Bz-CH). ¹³C{¹H} NMR (CDCl₃): 158.2, 148.7, (s, quaternary), 146.5 (s, CH), 145.2, 141.7, 141.1, 140.9 (s, quaternary), 126.2 (s, CH), 125.3 (s, CH), 124.6 (s, CH), 122.8 (s, CH), 111.4 (s, quaternary).

Synthesis of 107

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 280 mg, 0.38 mmol), 4-(benzo[d]thiazol-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzTaPTBr, 263 mg, 0.75 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 220 mg (61%). ¹H NMR (CDCl₃): δ 9.07 (s, 2H, PT-CH), 8.41 (t, 2H, SDT-CH), 8.31 (d, ³J_(H-H)=9 Hz, 2H Bz-CH), 8.04 (d, ³J_(H-H)=9 Hz, 2H Bz-CH), 7.56 (m, ³J_(H-H)=8 Hz, 2H, Bz-CH), 7.51 (m, ³J_(H-H)=8 Hz, 2H, Bz-CH), 1.57 (m, 2H, CH), 1.4-1.1 (bm, 16H, CH₂), 0.9-0.8 (m, 12H, CH₃). Anal. Calcd. for C₄₈H₄₆N₈S₆Si: C, 60.34; H, 4.85; N, 11.73. Found: C, 58.1; H, 4.51; N, 12.2%. HRMS (EI) m/z, calcd for C₅₀H₄₈N₆S₆Si (M⁺): 954. found: 954. Absorbance: (CHCl₃) λ_(max)=620 nm, λ_(onset)=725 nm. (As Cast Film) λ_(max)=620, 660 nm, λ_(onset)=775 nm.

The UV-VIS-NIR absorption spectrum of 107 in CHCl₃ solution and of a film of 107 as-cast from CHCl₃ solution is shown in FIG. 7.

Example 8

Synthesis of 5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (Me₃Sn-CDT_(EH))

A dry three-neck round bottom flask was equipped with a Schlenk adapter, dropping funnel, and rubber septum. Under argon, compound CDT_(EH) (2 g, 4.96 mmol) was dissolved in dry THF (200 mL) and cooled −78° C. using a dry ice/acetone cold bath. A solution of t-butyllithium (1.7 M pentane, 3.21 mL, 5.46 mmol) diluted with dry pentane (30 mL) was then added dropwise over 20 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all lithium reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 2 hours. A solution of trimethyltin chloride (1.5 g, 7.5 mmol) in dry pentane (30 mL) was then added dropwise over 5 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all tin reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 1 hour and subsequently warmed to room temperature and stirred for a further 1 hour. The mixture was then poured into de-ionized water (300 mL) and the organic phase extracted with hexanes (3×100 mL). The organic phases were collected and washed with de-ionized water (5×100 mL), dried over magnesium sulphate, filtered, and concentrated to give the product as yellow oil. Yield 2.65 g (95%). ¹H NMR (500 MHz, CD₂Cl₂): δ 7.11 (m, 1H), 7.00 (m, 1H), 6.95 (m, 1H), 1.89 (m, 4H, C—CH₂), 1.1-0.8 (m, 18H, alkyl), 0.75 (m, 6H, alkyl), 0.60 (m, 8H, alkyl), 0.36 (s, d, 9H, ²J_(H-Sn)=57 Hz, Sn—CH₃).

Synthesis of 4-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (CDTPTBr)

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 520 mg, 1.76 mmol), 5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (Me₃Sn-CDT_(EH), 985 mg, 1.74 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), anhydrous xylenes (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a red-purple oil. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CH₂Cl₂ gradient. The second fraction was collected and all solvent was removed in vacuo to give the product as a deep-red oil. Recovered yield: 910 mg (85%). ¹H NMR (CD₂Cl₂): δ 8.62 (m, 1H, Th—CH), 8.56 (s, 1H, PT-CH), 7.34 (d, ³J_(H-H)=8 Hz, 1H Th—CH), 7.03 (m, ³J_(H-H)=6 Hz, 1H Th—CH), 2.04 (m, 2H, C—CH₂), 1.95 (m, 2H, C—CH₂), 1.00 (m, 8H, alkyl), 0.96 (m, 8H, alkyl), 0.73 (m, 4H, alkyl), 0.69 (m, 2H, alkyl), 0.61 (m, 8H, alkyl).

Synthesis of 108

In a N₂ filled glove box a 5 mL microwave tube was charged with Me₃Sn-BDT_(EH)-SnMe₃ (270 mg, 0.35 mmol), CDTPTBr (430 mg, 0.70 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 180 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃. All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 430 mg (81%). ¹H NMR (CDCl₃): δ 8.92 (s, 2H, PT-CH), 8.76 (m, 2H, Th—CH), 8.66 (m, 2H, Th—CH), 7.32 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.02 (m, ³ _(H)=5 Hz, 2H Th—CH), 4.36 (m, 4H, OCH), 2.09 (m, 4H, CH₂), 1.98 (m, 6H, CH₂), 1.85 (m, 2H, CH₂), 1.79 (m, 2H, CH₂), 1.72 (m, 2H, CH₂), 1.62 (m, 2H, CH₂), 1.51 (m, 8H, CH₂), 1.14 (m, 6H, CH₃), 1.00 (m, 36H, CH₂, CH₃), 0.75 (m, 12H, CH₃), 0.62 (m, 18H, CH₃). ¹³C{¹H} NMR (CDCl₃): 160.41, 159.75, 155.15, 148.10, 147.79, 144.80, 143.99 (s, quaternary), 142.73 (s, PT-CH), 141.39, 136.95, 136.75, 133.30, 129.47 (s, quaternary), 127.88, 127.39, 122.53, 121.97 (s, CH), 119.22 (s, quaternary), 76.27 (s, OCH₂), 53.88, 43.35, 43.12, 40.81, 35.28, 35.25, 32.23, 30.68, 29.37, 28.66, 28.52, 27.49, 27.40, 24.02, 23.27, 22.78, 14.31, 14.07, 14.02, 11.52, 10.78, 10.63. Anal. Calcd. for C₈₆H₁₁₂N₆O₂S₈: C, 68.03; H, 7.43; N, 5.53. Found: C, 67.9; H, 7.22; N, 5.63%. Absorbance: (CHCl₃) λ_(max)=635 nm, λ_(onset)=715 nm. (As Cast Film) λ_(max)=640, 670 nm, λ_(onset)=790 nm.

The UV-VIS-NIR absorption spectrum of 108 in CHCl₃ solution and of a film of 108 as-cast from CHCl₃ solution is shown in FIG. 8.

Example 9

Synthesis of 5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (Me₃Sn-CDT_(EH))

A dry three-neck round bottom flask was equipped with a Schlenk adapter, dropping funnel, and rubber septum. Under argon, compound CDT_(EH) (2 g, 4.96 mmol) was dissolved in dry THF (200 mL) and cooled −78° C. using a dry ice/acetone cold bath. A solution of t-butyllithium (1.7 M pentane, 3.21 mL, 5.46 mmol) diluted with dry pentane (30 mL) was then added dropwise over 20 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all lithium reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 2 hours. A solution of trimethyltin chloride (1.5 g, 7.5 mmol) in dry pentane (30 mL) was then added dropwise over 5 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all tin reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 1 hour and subsequently warmed to room temperature and stirred for a further 1 hour. The mixture was then poured into de-ionized water (300 mL) and the organic phase extracted with hexanes (3×100 mL). The organic phases were collected and washed with de-ionized water (5×100 mL), dried over magnesium sulphate, filtered, and concentrated to give the product as yellow oil. Yield 2.65 g (95%). ¹H NMR (500 MHz, CD₂Cl₂): δ 7.11 (m, 1H), 7.00 (m, 1H), 6.95 (m, 1H), 1.89 (m, 4H, C—CH₂), 1.1-0.8 (m, 18H, alkyl), 0.75 (m, 6H, alkyl), 0.60 (m, 8H, alkyl), 0.36 (s, d, 9H, ²J_(H-Sn)=57 Hz, Sn—CH₃).

Synthesis of CDT_(EH)PhNPh₂

In a N₂ filled glove box a 20 mL glass tube was charged with 4-bromotriphenylamine (404 mg, 1.25 mmol), (Me₃Sn-CDT_(EH), 700 mg, 1.24 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), anhydrous xylenes (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (500 mL). All volatiles were removed in vacuo to give the crude product as an orange oil. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CH₂Cl₂ gradient. The second fraction was collected and all solvent was removed in vacuo to give the product as an orange oil. The product was dried under high vacuum for 24 hours. Recovered yield: 658 mg (82%). ¹H NMR (CD₂Cl₂): δ 7.47 (m, 2H), 7.27 (m, 4H), 7.15 (m, 1H, CDT), 7.14 (m, 1H, CDT), 7.11 (m, 4H), 7.05 (m, 4H), 6.97 (m, 1H, CDT), 1.91 (m, 4H), 1.01 (m, 10H), 0.95 (m, 4H), 0.93 (m, 2H), 0.76 (m, 3H), 0.73 (m, 3H), 0.68 (m, 2H), 0.63 (m, 3H), 0.61 (m, 3H). Anal. Calcd. for C₄₃H₅₁N₁S₂: C, 79.95; H, 7.96; N, 2.17. Found: C, 79.9; H, 7.99; N, 2.50%.

Synthesis of Me₃Sn-CDT_(EH)PhNPh₂

A dry three-neck round bottom flask was equipped with a Schlenk adapter, dropping funnel, and rubber septum. Under argon, compound CDT_(EH)PhNPh₂ (630 mg, 0.98 mmol) was dissolved in dry THF (100 mL) and cooled −78° C. using a dry ice/acetone cold bath. A solution of t-butyllithium (1.7 M pentane, 0.69 mL, 1.17 mmol) diluted with dry pentane (30 mL) was then added dropwise over 20 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all lithium reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 2 hours. A solution of trimethyltin chloride (293 mg, 1.47 mmol) in dry pentane (30 mL) was then added dropwise over 5 minutes via a dropping funnel. The dropping funnel was rinsed with dry pentane (30 mL) to ensure all tin reagent was transferred to the reaction vessel. The reaction was stirred at −78° C. under argon for 1 hour and subsequently warmed to room temperature and stirred for a further 2 hours. The mixture was then poured into de-ionized water (300 mL) and the organic phase extracted with diethyl ether (3×200 mL). The organic phases were collected and washed with de-ionized water (5×200 mL), dried over magnesium sulphate, filtered, and concentrated to give the product as red oil. The product was dried under high vacuum for 24 hours. Yield 780 mg (95%). ¹H NMR (CD₂Cl₂): δ 7.46 (m, 2H), 7.27 (m, 4H), 7.13 (m, 1H, CDT), 7.11 (m, 4H), 7.04 (m, 4H), 7.01 (m, 1H, CDT), 1.88 (m, 4H), 0.99 (m, 14H), 0.88 (m, 4H), 0.74 (m, 6H), 0.64 (m, 3H), 0.60 (m, 3H), 0.37 (m, 9H).

Synthesis of BrPT-CDT_(EH)PhNPh₂

In a N₂ filled glove box a 5 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 140 mg, 0.47 mmol), Me₃Sn-CDT_(EH)PhNPh₂ (385 mg, 0.48 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), anhydrous xylenes (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a dark solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. The product eluted as a large blue fraction at 60:40 hexanes/CHCl₃ (5% Et₃N). The fractions were collected and all solvent was removed in vacuo to give the product as a purple film. The product was then dissolved in a minimal amount of CHCl₃ and stirred for 5 minutes. All solvent was then removed and the product dried under high vacuum for 24 hours. The product was obtained as a purple solid. Recovered yield: 290 mg (71%). ¹H NMR (CDCl₃): δ 8.59 (s, 1H, PT), 8.57 (m, J=6 Hz, 1H CDT), 7.49 (m, ³J_(H-H)=5 Hz, 2H), 7.29 (m, ³J_(H-H)=8 Hz, 4H), 7.15 (m, 5H), 7.08 (m, ³J_(H-H)=8 Hz, 4H), 2.05 (m, 2H), 1.95 (m, 2H), 0.99 (m, 16H), 0.81 (m, 2H), 0.73 (m, 3H), 0.64 (m, 9H).

Synthesis of 109

In a N₂ filled glove box a 5 mL microwave tube was charged with Me₃Sn-BDT_(c6)-SnMe₃ (100 mg, 0.14 mmol), BrPT-CDT_(EH)PhNPh₂ (240 mg, 0.28 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N). All volatiles were removed in vacuo to give the crude product as a dark solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a dark purple film was obtained. The film was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as a dark metallic flakey solid was obtained. Recovered yield: 250 mg (92%). ¹H NMR (CD₂Cl₂): δ 8.86 (s, 2H, BDT), 8.73 (s, 2H, PT), 8.71 (m, J=6 Hz, 2H, CDT), 7.52 (m, 2H, Ph), 7.50 (m, 2H, Ph), 7.23 (m, ³J_(H-H)=8 Hz, 8H, Ph), 7.22 (br s, 2H, CDT), 7.13 (m, ³J_(H-H)=8 Hz, 8H, Ph), 7.07 (m, 8H, Ph), 4.46 (t, ³J_(H-H)=6 Hz, 4H, OCH₂), 2.09 (m, 4H), 2.01 (m, 8H), 1.73 (m, 4H), 1.48 (m, 8H), 1.08-0.94 (m, 34H), 0.84 (m, 6H), 0.74 (m, 6H), 0.66 (m, 18H). ¹³C{¹H} NMR (CD₂Cl₂): 162.33, 159.95, 155.67, 148.66, 148.30. 148.03, 147.99, 147.78, 145.15, 144.89 (quaternary), 143.26 (BDT-CH), 142.14, 137.55, 136.13, 133.83, 130.25 (quaternary), 129.92 (Ph-CH), 129.51 (quaternary), 128.52 (t, CDT-CH), 126.75, 125.23, 124.05, 123.87 (Ph-CH), 122.18 (PT-CH), 119.49 (quaternary), 118.36 (t, CDT-CH), 74.88 (OCH₂), 54.85 (CDT-bridge), 43.71, 43.64 (d, 2-ethylhexyl-CH), 36.00, 34.82, 34.77, 34.75, 32.37, 31.22, 29.27, 29.10, 28.15, 28.05, 26.50, 23.42, 23.40 (CH₂), 14.53, 14.42, 14.37, 11.15, 11.04 (CH₃). Anal. Calcd. for C₁₁₈H₁₃₄N₈O₂S₈: C, 72.57; H, 6.92; N, 5.74. Found: C, 72.8; H, 6.55; N, 5.24%. Absorbance: (CHCl₃) λ_(max)=675 nm, λ_(onset)=766 nm, ∈=56 000 cm⁻¹ M⁻¹. (As Cast Film) λ_(max)=705, 665 nm, λ_(onset)=820 nm.

The UV-VIS-NIR absorption spectrum of 109 in CHCl₃ solution and of a film of 109 as-cast from CHCl₃ solution is shown in FIG. 9.

Example 10

Synthesis of 110

In a N₂ filled glove box a 5 mL microwave tube was charged with Me₃Sn-BDT_(EH)-SnMe₃ (300 mg, 0.39 mmol), HexTPTBr (326 mg, 0.85 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice to ensure complete removal of all trace impurities and by-products. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as a purple solid. Recovered yield: 390 mg (96%). ¹H NMR (CDCl₃): δ 8.45 (s, 2H, PT-CH), 8.31 (s, 2H, BDT-CH), 8.19 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.66 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 4.22 (br m, 4H, OCH), 2.76 (m, 4H, Th—CH₂), 1.86 (br m, 4H, CH₂), 1.79-1.60 (m, 10H, CH₂), 1.54 (br m, 8H, CH₂), 1.39 (br m, 4H, CH₂), 1.33 (br m, 8H, CH₂), 1.16 (t, ³J_(H-H)=8 Hz, 6H, CH₃), 1.06 (t, ³J_(H-H)=5 Hz, 6H, CH₃), 0.92 (m, ³J_(H-H)=8 Hz, 6H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.37, 152.45, 147.74, 146.25, 144.27, 142.84 (s, quaternary), 141.48 (CH), 138.81, 135.52, 132.86 (s, quaternary), 132.11 (CH), 128.70 (s, quaternary), 126.10, 122.13 (CH), 119.28 (s, quaternary). Anal. Calcd. for C₅₆H₆₈N₆O₂S₆: C, 64.08; H, 6.53; N, 8.01. Found: C, 64.0; H, 6.35; N, 8.10%. Absorbance: (CHCl₃) λ_(max)=560 nm, λ_(onset)=670 nm. (As Cast Film) λ_(max)=590, 630 nm, λ_(onset)=725 nm.

The UV-VIS-NIR absorption spectrum of 110 in CHCl₃ solution and of a film of 110 as-cast from CHCl₃ solution is shown in FIG. 10.

Example 11

Synthesis of 111

In a N₂ filled glove box a 5 mL microwave tube was charged with Me₃Sn-BDT_(EH)-SnMe₃ (191 mg, 0.27 mmol), HexTTPTBr (230 mg, 0.50 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was transferred to a 500 mL round bottom flask using CHCl₃ and all volatiles removed in vacuo to give the crude product as a purple solid. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH, Acetone, iPrOH, hexanes using a soxhelt apparatus and then dried under vacuum for 24 hours. The product was collected as a purple solid. Recovered yield: 170 mg (57%). Compound III exhibits very low solubility in organic solvents (<5 mg/mL in CHCl₃) and minimal movement on silica-gel.

The UV-VIS-NIR absorption spectrum of 111 in CHCl₃ solution and of a film of 111 as-cast from CHCl₃ solution is shown in FIG. 11.

Example 12

Synthesis of 112

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-di-2-hexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(Hex)-SnMe₃, 500 mg, 0.73 mmol), 7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThPTBr, 560 mg, 1.46 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 480 mg (69%). ¹H NMR (CDCl₃): δ 8.60 (s, 2H, PT-CH), 8.36 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.15 (t, 2H, SDT-CH), 6.90 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 2.90 (t, ³J_(H-H)=7 Hz, 4H Th—CH₂), 1.79 (tt, ³J_(H-H)=7 Hz, 4H, CH₂), 1.56 (m, 4H, CH), 1.44 (br m, 8H, CH₂), 1.36 (m, 8H, CH₂), 1.32 (m, 8H, CH₂), 1.10 (m, 4H, SiCH₂), 0.92 (m, 6H, CH₃), 0.88 (m, 6H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.25, 152.97, 150.47, 147.69, 145.35, 143.97 (s, quaternary), 139.96 (s, CH), 139.10, 138.65 (s, quaternary), 131.96 (s, CH), 130.63 (s, CH), 126.30 (s, CH), 119.99 (s, quaternary), 32.99 (s, CH₂), 31.57 (s, CH₂), 31.51 (s, CH₂), 30.39 (s, CH₂), 30.56 (s, CH₂), 28.81 (s, CH₂), 24.29 (s, CH₂), 26.61 (s, CH₂), 22.57 (s, CH₂), 14.11 (s, CH₂), 14.07 (s, CH₃), 11.99 (s, CH₃). Anal. Calcd. for C₅₀H₆₀N₆S₆Si: C, 62.20; H, 6.26; N, 8.70. Found: C, 62.2; H, 6.16; N, 8.67%. Absorbance: (CHCl₃) λ_(max)=600 nm, λ_(onset)=715 nm. (As Cast Film) λ_(max)=625, 675 nm, λ_(onset)=795 nm.

The UV-VIS-NIR absorption spectrum of 112 in CHCl₃ solution and of a film of 112 as-cast from CHCl₃ solution is shown in FIG. 12.

Example 13

Synthesis of 113

In a N₂ filled glove box a 20 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-dihexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(HEX)-SnMe₃, 394 mg, 0.57 mmol), 7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThPTBr, 530 mg, 1.14 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 520 mg (80%). ¹H NMR (CDCl₃): δ 8.64 (s, 2H, PT-CH), 8.44 (m, 2H, Th—CH), 8.11 (m, 2H, SDT-CH), 7.16 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.15 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.72 (m, 2H, Th—CH), 2.81 (t, ³J_(H-H)=7 Hz, 4H Th—CH₂), 1.73 (tt, ³J_(H-H)=6 Hz, 4H, CH₂), 1.57 (m, 4H, CH₂), 1.41 (br m, 8H, CH₂), 1.33 (br m, 16H, CH₂), 1.10 (m, 4H, CH₂), 0.93 (m, 6H, CH₃), 0.88 (m, 6H, CH₃). Absorbance: (CHCl₃) λ_(max)=630 nm, λ_(onset)=735 nm. (As Cast Film) λ_(max)=660, 715 nm, λ_(onset)=800 nm.

The UV-VIS-NIR absorption spectrum of 113 in CHCl₃ solution and of a film of 113 as-cast from CHCl₃ solution is shown in FIG. 13.

Example 14

Synthesis of 114

In a N₂ filled glove box a 5 mL microwave tube was charged with 5,5′-Bis(trimethylstannyl)-3,3′-di-2-dodecilsilylene-2,2′-bithiophene (Me₃Sn-SDT_(C12)-SnMe₃, 370 mg, 0.43 mmol), 7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThPTBr, 400 mg, 0.86 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 500 mg (89%). ¹H NMR (CDCl₃): δ 8.57 (s, 2H, PT-CH), 8.36 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.09 (m, 2H, SDT-CH), 7.13 (d, ³J_(H-H)=5 Hz, 4H Th—CH), 6.71 (m, 2H, Th—CH), 2.81 (m, 4H Th—CH₂), 1.71 (m, 4H, CH₂), 1.59 (m, 4H, CH₂), 1.43 (br m, 8H, CH₂), 1.35 (m, 12H, CH₂), 1.24 (br m, 28H, CH₂), 1.11 (m, 4H, CH₂), 0.93 (m, 6H, CH₃), 0.85 (m, 6H, CH₃). Anal. Calcd. for C₇₀H₈₈N₆S₈Si: C, 64.77; H, 6.83; N, 6.47. Found: C, 64.5; H, 6.90; N, 6.56%. Absorbance: (CHCl₃) λ_(max)=630 nm, λ_(onset)=750 nm. (As Cast Film) λ_(max)=655, 715 nm, λ_(onset)=825 nm.

The UV-VIS-NIR absorption spectrum of 114 in CHCl₃ solution and of a film of 114 as-cast from CHCl₃ solution is shown in FIG. 14.

Example 15

Synthesis of 115 (G9-C)

In a N₂ filled glove box a 20 mL microwave tube was charged with 4,4-bis(2-ethylhexyl)-2,6-bis(trimethylstannyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene (Me₃Sn-CDT_(EH)-SnMe₃, 520 mg, 0.71 mmol), 7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (HexThThPTBr, 637 mg, 1.37 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 710 mg (85%). ¹H NMR (CDCl₃): δ 8.83 (s, 2H, PT-CH), 8.58 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 8.10 (t, 2H, SDT-CH), 7.25 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 7.19 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 6.76 (m, 2H, Th—CH), 2.84 (m, 4H Th—CH₂), 2.08 (m, 4H, CH₂), 1.72 (tt, ³J_(H-H)=6 Hz, 4H, CH₂), 1.42 (m, 4H, CH), 1.35 (m, 8H, CH₂), 1.05-1.00 (br m, 14H, CH₂), 0.92 (m, 6H, CH₂), 0.84 (m, 4H, CH₂), 0.66 (m, 12H, CH₃). Absorbance: (CHCl₃) λ_(max)=655 nm, λ_(onset)=765 nm. (As Cast Film) λ_(max)=680, 740 nm, λ_(onset)=845 nm.

The UV-VIS-NIR absorption spectrum of 115 in CHCl₃ solution and of a film of 115 as-cast from CHCl₃ solution is shown in FIG. 15.

Example 16

Synthesis of BrPT-SDT-PTBr

In a N₂ filled glove box a 20 mL glass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.27 g, 4.31 mmol), 5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 800 mg, 1.07 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon cap. The reaction mixture was heated to 100° C. for 15 hours, during which a color change from yellow to purple was observed. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a dark sticky solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. The product eluted as a purple solution at 80% CHCl₃ (5% Et₃N). After fraction collection and solvent removal, the solid product was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as green metallic coloured powder. Recovered yield: 550 mg (60%). ¹H NMR (CDCl₃): δ 8.76 (s, 2H, PT-CH), 8.66 (s, 2H, SDT-CH), 1.52 (m, 2H, CH), 1.39 (m, 4H, CH₂), 1.31 (m, 4H, CH₂), 1.16 (m, 8H, CH₂), 1.06 (m, 4H, CH₂), 0.85 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 156.38, 153.85, 147.98, 147.66, 147.49 (s, quaternary), 146.03 (s, CH), 143.94 (s, quaternary), 135.99 (s, CH), 107.64 (s, quaternary), 36.02 (s, CH), 35.76 (s, CH₂), 22.97 (s, CH₂), 22.93 (s, CH₂), 20.92 (s, CH₂), 17.64 (s, CH₂), 14.15 (s, CH₃). 10.80 (s, CH₃).

Synthesis of 116

In a N₂ filled glove box a 5 mL microwave tube was charged with BrPT-SDT-PTBr (420 mg, 0.50 mmol), 5′-hexyl-2,2′-bithiophene-5-trimethylstannane (450 mg, 1.09 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with a Teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo to give the crude product as a purple solid. The material was then loaded onto silica and purified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solvent removal a purple solid was obtained. Purification by silica column chromatography was carried out twice. The solid was slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as purple solid. Recovered yield: 475 mg (81%). ¹H NMR (CDCl₃): δ 8.72 (t, 2H, SDT-CH), 8.70 (s, 2H, PT-CH), 7.95 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 7.16 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 7.11 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 6.73 (d, ³J_(H-H)=5 Hz, 2H, Th—CH), 2.83 (t, ³J_(H-H)=8 Hz, 4H Th—CH₂), 1.72 (h, ³J_(H-H)=6 Hz, 4H, CH₂), 1.62 (m, 2H, CH), 1.41 (m, 8H, CH₂), 1.35 (m, 12H, CH₂), 1.28 (m, 8H, CH₂), 1.18 (m, 4H, SiCH₂), 0.92-0.83 (m, 18H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.56, 153.65, 147.98, 147.43, 146.27, 145.76, 144.77, 140.43 (s, quaternary), 139.63 (s, PT-CH), 135.19, 134.85 (s, quaternary), 134.44 (s, SDT-CH), 128.42 (s, Th—CH), 125.01 (s, Th—CH), 123.99 (s, Th—CH), 123.85 (s, Th—CH), 119.59 (s, quaternary), 36.10 (s, CH), 35.86 (s, CH₂), 31.57 (s, Si—CH₂), 30.26 (s, Th—CH₂), 29.08 (s, CH₂), 29.01 (s, CH₂), 28.80 (s, CH₂), 23.08 (s, CH₂), 22.59 (s, CH₂), 17.73 (s, CH₂), 14.26 (s, CH₃), 14.09 (s, CH₃), 10.88 (s, CH₃). Absorbance: (CHCl₃) λ_(max)=655 nm, λ_(onset)=715 nm, c=37400 cm⁻¹ M⁻¹. (As Cast Film) λ_(max)=655, 725 nm, λ_(onset)=815 nm.

The UV-VIS-NIR absorption spectrum of 116 in CHCl₃ solution and of a film of 116 as-cast from CHCl₃ solution is shown in FIG. 16.

Example 17 Determination of HOMO-LUMO Values

Electrochemistry:

All electrochemical measurements were performed using CHI instrument model 730B in a standard three-electrode, one compartment configuration equipped with Ag/AgCl electrode, Pt wire and Glassy carbon electrode (dia. 3 mm), as the pseudo reference, counter electrode and working electrode respectively. Glassy carbon electrodes were polished with alumina. The cyclic voltammetry (CV) experiments were performed in anhydrous dichloromethane (DCM) solution with 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte at scan rate 100 mV/s unless otherwise stated. All electrochemical solutions were purged with dry Ar for 15 minutes at least to deoxygenate the system. Under these conditions, a Fc/Fc⁺ standard was calibrated to be 0.40 V. In solution, monomer concentration was about ˜10⁻³ M.

Calculations:

All calculations were performed using the Gaussian 03 program. Optimized gas-phase structures were obtained using the density functional theory (DFT) method B3LYP in conjunction with 6-31G(d,p) basis set, i.e., B3LYP/6-31G(d,p). California NanoSystems Institute at UCSB is acknowledged for computational resources.

FIG. 17 shows highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values measured electrochemically and calculated using the method above for example compounds 101, 103, 104, 105, 106, 108.

Example 18 General Procedures for Fabrication of Devices

Device Fabrication:

Indium tin oxide (ITO) substrates were prepared by wet cleaning and then UV/ozone treatment. A 50 nm hole injection layer (Plextronics Plexcore OC AQ-1300) was spin coated on top of an ITO substrate. A solution of filtered (1 μm Whatman PTFE filter) 103:PC₇₁BM with varied ratios in chloroform was spin coating onto the ITO/PEDOT:PSS substrate at varied spin speeds for different thicknesses. The PC₇₁BM was 99% pure and used as received from Solenne, and chloroform was used as received from Sigma-Aldrich Inc. The 103:PC₇₁BM films thicknesses were determined by profilometry. Devices had a 13 mm² area Al cathode evaporated on top of the 103:PC₇₁BM film in a vacuum (˜10⁻⁶ torr) at rate of 1 Å sec⁻¹ for 10 nm and then 2.5 Å sec⁻¹ with a total thickness of approximately 100 nm. All fabrication and testing were carried out inside a nitrogen atmosphere drybox.

Device Testing.

Device J-V curves were measured with a Keithley 2602 source-measure unit while illuminated with a simulated 100 mWcm⁻² AM 1.5 G light source using a 300 W Xe arc lamp with an AM1.5 global filter. Solar-simulator illumination intensity was measured using a standard silicon photovoltaic with a protective KG1 filter calibrated by the National Renewable Energy Laboratory. IPCE spectra measurements were made with a 75 W Xe source, monochromator, optical chopper, lock-in amplifier, and a National Institute of Standards and Technology traceable silicon photodiode for monochromatic power-density calibration. Mismatch factors of the integrated IPCE for the devices were calculated to be less than 3.1%

Example 19 Organic Solar Cell Device Using Compound 103

FIG. 18 shows the energy level diagram of a standard bulk-heterojunction solar cell device fabricated using compound 103.

Example 20

FIG. 19 and Table 1 show current-voltage plots of bulk heterojunction devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were cast from 2% chloroform solutions at 1500 rpm. Active layer thickness=75 nm.

Example 21

FIG. 20 and Table 2 show the current-voltage plots of BHJ devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 1500 rpm. Active layer thickness=75 nm. Devices annealed at 110° C. for 2 minutes under N₂.

Example 22

FIG. 21 and Table 3 show current-voltage plots of bulk heterojunction devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were cast from 2% chloroform solutions at 2500 rpm. Active layer thickness=85 nm.

Example 23

FIG. 22 and Table 4 show the current-voltage plots of BHJ devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 2500 rpm. Active layer thickness=85 nm. Devices annealed at 110° C. for 2 minutes under N₂.

Example 24

FIG. 23 and Table 5 show current-voltage plots of bulk heterojunction devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were cast from 2% chloroform solutions at 3500 rpm. Active layer thickness=105 nm.

Example 25

FIG. 24 and Table 6 show the current-voltage plots of BHJ devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 3500 rpm. Active layer thickness=105 nm. Devices annealed at 110° C. for 2 minutes under N₂.

Example 26

FIG. 25 shows the best current-voltage plots of BHJ devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layer composition was 60:40 103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 2500 rpm. Active layer thickness=85 nm. Device annealed at 110° C. for 2 minutes under N₂.

Example 27

FIG. 26 shows the EQE spectra of best BHJ devices fabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layer composition was 60:40 103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 2500 rpm. Active layer thickness=85 nm. Device annealed at 110° C. for 2 minutes under N₂.

Example 28

FIG. 27 shows the UV-vis-NIR absorption spectra of a 60:40 (w/w) blend of 103:PC₇₁BM as-cast film from CHCl₃ (solid), and annealed film 110° C. 2 minutes (large dashed).

Example 29 Field Effect Transistor

FIG. 28 shows an example of an organic field effect transistor using material 103. Films were spun cast from 0.5% w/V in chloroform onto cleaned SiO₂ substrate at 2000 rpm for 40 s. An Au electrode was thermally deposited at 4×10⁻⁷ Torr for 85 nm using a shadow mask with dimensions of L=40 μm and W=1 mm. For annealed samples, samples were annealed on a hotplate at 120° C. for 15 minutes prior to electrode deposition.

FIG. 28 shows the FET device output (top) and transfer (bottom) current-voltage curves

The average FET mobility of example compound 103 for as-cast film=7.61×10⁻⁰³ cm²/Vs, while the average FET mobility of example compound 103 for annealed film=1.11×10⁻⁰³ cm²/Vs.

Example 30 Proposed Synthesis of Pyridaloxadiazole (PO) Organic Intermediate

The pyridaloxadiazole (PO) core structure is synthesized as outlined above. For relevant literature see: M. Leclerc et al. Journal of the American Chemical Society, 2008, 130, 732.; R. A. J. Janssen et al. Chemistry of Materials, 2009, 21, 4669.; T. M. Swager et al. Macromolecules, 2008, 41, 5559.; March's Advanced Organic Chemistry, 5^(th) Ed., Wiley, 2001.

The disclosures of all publications, patents, patent applications and published patent applications referred to herein by an identifying citation are hereby incorporated herein by reference in their entirety.

Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is apparent to those skilled in the art that certain changes and modifications will be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention. 

1. An electronic or optoelectronic device comprising a non-polymeric compound, said compound incorporating one or more groups of Formula A:

where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device, where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl, and either X₁ is CH and Y₁ is N, or X₁ is N and Y₁ is CH.
 2. An electronic or optoelectronic device according to claim 1, wherein said device is a solar cell.
 3. An electronic or optoelectronic device according to claim 1, wherein said group of Formula A is a pyridalthiadiazole group, a pyridaloxadiazole group, or a pyridaltriazole group.
 4. A compound of Formula II:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; n is an integer between 0 and 5, inclusive; A₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups; each B₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups; and each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.
 5. A compound according to claim 4 of Formula IIa, Formula IIb, or Formula IIc:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where A₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; B₁ is independently selected from a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group; each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group; and n is an integer between 0 and 5 inclusive.
 6. The compound of claim 5, wherein A₁ is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′ silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl.
 7. The compound of claim 5, wherein B₁ is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
 8. A compound of Formula I:

wherein X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; A₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each B₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group.
 9. The compound of claim 8, wherein A₁ is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl.
 10. The compound of claim 8, wherein each B₁ is selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
 11. A compound of claim 8 of the following formulas Ia, Ib, or Ic:


12. A compound of Formula III:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where H₁ is selected from A₁, —B₁—B₂, -A₁-B₁—B₂, or

n is an integer between 0 and 5, inclusive; A₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups; each B₁ (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and each B₂ (when present) is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group.
 13. A compound of claim 12 of Formula IIIa, Formula IIIb, Formula IIIc, or Formula IIId:


14. A compound of Formula IV-V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N; M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; K₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups; each E₁ is independently either absent, or selected from substituted or unsubstituted aryl or heteroaryl groups; each D₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group.
 15. A compound of claim 14 of Formula IVa or Formula IVb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each D₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; and each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group.
 16. A compound of claim 14 of Formula Va or Formula Vb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each D₁ and E₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; and each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group.
 17. A compound of Formula VI-VII:

where the moiety

is selected from

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ is CH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁, X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, and when X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, and when X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ is CH, and when X₄ is CH, Y₄ is N; where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; each F₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups; each G₁ is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroaryl group.
 18. A compound of claim 17 of Formula VIa or Formula VIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where each F₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each G₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; and each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group.
 19. A compound of claim 17 of Formula VIIa or Formula VIIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where each F₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each G₁ is independently selected from C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; and each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl group.
 20. A compound selected from Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10:

where: M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; n is an integer from 0 to 5 inclusive; m is an integer from 0 to 5 inclusive; R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, and C₂-C₁₆ alkynyl; J is selected from CH and N; X is S, O, or NH when X is CH; and X is S when J is N; R₄ is C₆-C₃₀ aryl optionally substituted with one or more C₁-C₁₆ alkyl groups; R₆ is selected from aryl, perfluoroaryl, or C₆-C₃₀ aryl optionally perfluorinated or optionally substituted with one or more C₁-C₁₆ alkyl groups; and each DONOR is independently selected from:

where X is C or Si; A is N or P; R₁₁ is selected from C₁-C₁₆ alkyl; R₁₂ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl; R₁₃ is selected from C₁-C₁₆ alkyl or C₆-C₂₀ aryl; R₁₄ is selected from C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, —C(═O)—O—C₁-C₁₆ alkyl, or —O—C(═O)—C₁-C₁₆ alkyl; and R₁₅ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl; and R₁₆ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl, C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl.
 21. An electronic or optoelectronic device comprising a non-polymeric compound of claim 4, where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
 22. An electronic or optoelectronic device comprising a non-polymeric compound of claim 5, where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
 23. An electronic or optoelectronic device comprising a non-polymeric compound of claim 6, where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
 24. An electronic or optoelectronic device comprising a non-polymeric compound of claim 7, where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
 25. An electronic or optoelectronic device comprising a non-polymeric compound of claim 8, where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
 26. A device comprising: 1) a first hole-collecting electrode optionally coated onto a transparent substrate; 2) an optional layer or layers adjacent to the first electrode, such as an electron-blocking, exciton-blocking, or hole-transporting layer; 3) a layer comprising a mixture of an electron acceptor material and an organic non-polymeric electron donor, said electron donor comprising a compound of claim 4; 4) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and 5) a second electron-collecting electrode.
 27. (canceled)
 28. A device comprising: 1) a first hole-collecting electrode optionally coated onto a transparent substrate; 2) an optional layer or layers adjacent to the first electrode, such as an electron-blocking, exciton-blocking, or hole-transporting layer; 3) a layer comprising a mixture of an organic non-polymeric electron acceptor material and an electron donor, said electron acceptor comprising a compound of claim 4; 4) an optional layer or layers such as hole-blocking, exciton-blocking, or electron-transporting layers; and 5) a second electron-collecting electrode. 29-32. (canceled)
 33. The device of claim 1, wherein the non-polymeric compound has a solubility of at least about 5 mg/mL in an organic solvent.
 34. The device of claim 33, wherein the organic solvent is selected from chloroform, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran, and carbon disulfide.
 35. The device of claim 1, wherein the device is prepared by solution processing of the non-polymeric compound. 